CN103459341A - Glass substrate with sealing material layer, organic el device using same, and manufacturing method for electronic device - Google Patents
Glass substrate with sealing material layer, organic el device using same, and manufacturing method for electronic device Download PDFInfo
- Publication number
- CN103459341A CN103459341A CN2012800180130A CN201280018013A CN103459341A CN 103459341 A CN103459341 A CN 103459341A CN 2012800180130 A CN2012800180130 A CN 2012800180130A CN 201280018013 A CN201280018013 A CN 201280018013A CN 103459341 A CN103459341 A CN 103459341A
- Authority
- CN
- China
- Prior art keywords
- seal
- sealing materials
- glass
- sealing
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011521 glass Substances 0.000 title claims abstract description 1127
- 239000003566 sealing material Substances 0.000 title claims abstract description 853
- 239000000758 substrate Substances 0.000 title claims abstract description 308
- 238000004519 manufacturing process Methods 0.000 title claims description 99
- 239000000843 powder Substances 0.000 claims abstract description 477
- 239000000945 filler Substances 0.000 claims abstract description 138
- 230000003746 surface roughness Effects 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 239000010410 layer Substances 0.000 claims description 416
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 272
- 239000000049 pigment Substances 0.000 claims description 143
- 238000000034 method Methods 0.000 claims description 121
- 239000002245 particle Substances 0.000 claims description 74
- 239000000463 material Substances 0.000 claims description 71
- 230000001678 irradiating effect Effects 0.000 claims description 62
- 239000012298 atmosphere Substances 0.000 claims description 53
- 238000007789 sealing Methods 0.000 claims description 51
- 150000001875 compounds Chemical class 0.000 claims description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 40
- 239000011248 coating agent Substances 0.000 claims description 40
- 238000000576 coating method Methods 0.000 claims description 40
- 229910052799 carbon Inorganic materials 0.000 claims description 32
- 239000011230 binding agent Substances 0.000 claims description 28
- 239000011247 coating layer Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 238000010304 firing Methods 0.000 claims description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims description 20
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 18
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 18
- 229910052797 bismuth Inorganic materials 0.000 claims description 17
- -1 poly ethylene Polymers 0.000 claims description 10
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 229910052845 zircon Inorganic materials 0.000 claims description 7
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052596 spinel Inorganic materials 0.000 claims description 6
- 239000011029 spinel Substances 0.000 claims description 6
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 2
- 238000005401 electroluminescence Methods 0.000 claims 3
- 230000009970 fire resistant effect Effects 0.000 abstract 2
- 239000000203 mixture Substances 0.000 description 344
- 239000010408 film Substances 0.000 description 142
- 238000004031 devitrification Methods 0.000 description 122
- 230000008018 melting Effects 0.000 description 101
- 238000002844 melting Methods 0.000 description 101
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 72
- 238000002156 mixing Methods 0.000 description 55
- 239000002904 solvent Substances 0.000 description 53
- 238000010521 absorption reaction Methods 0.000 description 41
- 230000006378 damage Effects 0.000 description 40
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 39
- 230000003287 optical effect Effects 0.000 description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 230000000694 effects Effects 0.000 description 28
- 229910004298 SiO 2 Inorganic materials 0.000 description 26
- 230000005496 eutectics Effects 0.000 description 26
- 239000012299 nitrogen atmosphere Substances 0.000 description 25
- 239000011164 primary particle Substances 0.000 description 25
- 230000033228 biological regulation Effects 0.000 description 22
- 239000007789 gas Substances 0.000 description 22
- 238000007650 screen-printing Methods 0.000 description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 20
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 20
- 239000002994 raw material Substances 0.000 description 20
- 230000006641 stabilisation Effects 0.000 description 20
- 238000011105 stabilization Methods 0.000 description 20
- 238000012360 testing method Methods 0.000 description 20
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 18
- CUZKCNWZBXLAJX-UHFFFAOYSA-N 2-phenylmethoxyethanol Chemical compound OCCOCC1=CC=CC=C1 CUZKCNWZBXLAJX-UHFFFAOYSA-N 0.000 description 18
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical group C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 18
- 230000007774 longterm Effects 0.000 description 18
- 229960005323 phenoxyethanol Drugs 0.000 description 18
- 229910052726 zirconium Inorganic materials 0.000 description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 16
- 230000015556 catabolic process Effects 0.000 description 16
- 238000006731 degradation reaction Methods 0.000 description 16
- 230000007704 transition Effects 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 238000009826 distribution Methods 0.000 description 15
- 230000005855 radiation Effects 0.000 description 15
- 230000006978 adaptation Effects 0.000 description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 13
- 239000002253 acid Substances 0.000 description 13
- 239000003292 glue Substances 0.000 description 13
- 208000037656 Respiratory Sounds Diseases 0.000 description 12
- 239000010439 graphite Substances 0.000 description 12
- 229910002804 graphite Inorganic materials 0.000 description 12
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 12
- 238000004455 differential thermal analysis Methods 0.000 description 11
- 238000005457 optimization Methods 0.000 description 11
- 238000010298 pulverizing process Methods 0.000 description 11
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 230000007812 deficiency Effects 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 229910052748 manganese Inorganic materials 0.000 description 10
- 239000012528 membrane Substances 0.000 description 10
- 229910052700 potassium Inorganic materials 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000002050 diffraction method Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 229910003481 amorphous carbon Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910000314 transition metal oxide Inorganic materials 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 230000003685 thermal hair damage Effects 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 229910052788 barium Inorganic materials 0.000 description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 229930188620 butyrolactone Natural products 0.000 description 5
- 229910052792 caesium Inorganic materials 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 5
- 229940093476 ethylene glycol Drugs 0.000 description 5
- 229910000174 eucryptite Inorganic materials 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 229910052738 indium Inorganic materials 0.000 description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 5
- 239000003273 ketjen black Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 229910052863 mullite Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910052758 niobium Inorganic materials 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- 230000002093 peripheral effect Effects 0.000 description 5
- 229920000379 polypropylene carbonate Polymers 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 229910052706 scandium Inorganic materials 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 229910052712 strontium Inorganic materials 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 229910052727 yttrium Inorganic materials 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 229910000500 β-quartz Inorganic materials 0.000 description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 5
- 239000000470 constituent Substances 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 238000011835 investigation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000004382 potting Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000005394 sealing glass Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000004520 agglutination Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SDKTUKJXHDZWMB-UHFFFAOYSA-N phosphoric acid zirconium Chemical compound [Zr].P(O)(O)(O)=O SDKTUKJXHDZWMB-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B23/00—Re-forming shaped glass
- C03B23/20—Uniting glass pieces by fusing without substantial reshaping
- C03B23/24—Making hollow glass sheets or bricks
- C03B23/245—Hollow glass sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
- C03C17/04—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass by fritting glass powder
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/06—Joining glass to glass by processes other than fusing
- C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/842—Containers
- H10K50/8426—Peripheral sealing arrangements, e.g. adhesives, sealants
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/871—Self-supporting sealing arrangements
- H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
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Abstract
This glass substrate with a sealing material layer is equipped with a sealing material layer that is formed by sintering a sealing material, and is characterized in that: the sealing material includes at least an inorganic powder; the inorganic powder includes a glass powder and a fire resistant filler; the content of fire resistant filler in the inorganic powder is 10-35 vol. %; and the surface roughness (Ra) of the sealing material layer is less than 0.5[mu]m.
Description
Technical field
The present invention relates to the glass substrate of seal, sealing materials layer and use its organic EL device, process the glass substrate with the seal, sealing materials layer of (below, be called the laser sealing-in), and use its organic EL device in particular to being suitable for implementing sealing-in by laser.In addition, the present invention relates to the manufacture method of electron device, particularly relate to the method for manufacturing organic EL device by the laser sealing-in.
Background technology
In recent years, as two-d display panel, OLED display is attracted attention.OLED display has following advantage:, owing to can passing through direct voltage drive, therefore can make driving circuit simplify, and have view angle dependency unlike liquid-crystal display, therefore in addition because self is luminous brighter, and fast response time.Now, OLED display mainly is used in the miniature portable machines such as mobile telephone, expects to be applied to from now on extra-thin TV.It should be noted that, similarly, configuring the active components such as thin film transistor (TFT) and make the mode of its driving in each pixel is main flow for OLED display and liquid-crystal display.
OLED display consists of the anodes such as negative electrode, organic luminous layer, ITO, adhesivess etc. such as 2 sheet glass substrates, metals.All the time, as adhesives, using the organic resins such as epoxy resin with curability at low temperatures or ultraviolet curable resin is adhesives.But, with regard to organic resin is adhesives, it can't block the intrusion of gas fully.Therefore, if using organic resin is adhesives, can't keep the resistance to air loss of organic EL display interior, and as former thereby produce: the low organic luminous layer of water tolerance easily display characteristic deteriorated, OLED display is passed and deteriorated such unfavorable condition in time.Therefore in addition, although organic resin is adhesives, has advantages of and can at low temperatures glass substrate be bonded to each other, because water tolerance is low, in the situation that the life-time service OLED display, the reliability of indicating meter easily reduces.
On the other hand, with organic resin, be that adhesives is compared, the seal, sealing materials water tolerance excellence that comprises glass powder is suitable for guaranteeing the resistance to air loss of OLED display inside simultaneously.
But usually, the softening temperature of glass powder is more than 300 ℃, therefore be difficult to be applicable to OLED display.If describe particularly, in the situation that with above-mentioned seal, sealing materials by glass substrate sealing-in each other, need to be burnt till at the temperature more than the softening temperature of glass powder in the whole input of OLED display electric furnace, and make glass powder softening mobile.But the active component that OLED display is used only has the thermotolerance of 120～130 ℃ of left and right, if therefore adopt the method by glass substrate sealing-in each other, active component damages because of heat, and the display characteristic of OLED display can be deteriorated.In addition, luminous organic material also lacks thermotolerance, if therefore adopt the method by glass substrate sealing-in each other, luminous organic material damages because of heat, and the display characteristic of OLED display can be deteriorated.
The prior art document
Patent documentation
Patent documentation 1: No. 6416375 specification sheets of United States Patent (USP)
Patent documentation 2: No. 2006-315902 public Reported of TOHKEMY
Summary of the invention
Invention institute is the problem of solution just
In light of this situation, in recent years, as the method for sealing-in OLED display, studied the laser sealing-in.By the laser sealing-in, can be only part that should sealing-in be carried out to local heating, therefore can prevent the thermal degradation when of active component etc., and by glass substrate sealing-in each other.
In patent documentation 1,2, record the glass substrate of the field-emitter display content of laser sealing-in each other.But, in patent documentation 1,2, about the not record of state of concrete material formation, seal, sealing materials layer (burning till film), do not know that what kind of material forms, the state of seal, sealing materials layer is suitable for the laser sealing-in.It should be noted that, if improve the output rating of laser, even without making, material forms, suitableization of state of seal, sealing materials layer also can be carried out the laser sealing-in, but, in this situation, active component etc. are heated, and the display characteristic of OLED display is likely deteriorated.
Therefore, the 1st technical task of the present invention is, initiates out the glass substrate with the seal, sealing materials layer that can carry out the laser sealing-in by the laser of low output rating, improves thus the long-term reliability of OLED display etc.
In addition, the laser sealing-in is for example undertaken by following operation.At first, seal, sealing materials and material containing are mixed, make the seal, sealing materials paste.At this, material containing consists of organic binder bond and solvent usually.Next, by screen process press, point gum machine etc., along the neighboring of glass substrate, with frame-like coating seal, sealing materials paste, form coating layer on glass substrate.Then, burn till coating layer, form the seal, sealing materials layer on glass substrate, and seal, sealing materials layer and glass substrate are fixed.Then, make gained the glass substrate with the seal, sealing materials layer, with the glass substrate that is formed with organic EL etc., overlap, then along the seal, sealing materials layer, irradiating laser, carry out the laser sealing-in each other by glass substrate.
But, if burn till coating layer, the organic binder bond in material containing (Japanese original text: PVC one グ Le) is removed by burning.
On the other hand, seal, sealing materials self also comprises CO
2, H
2the gaseous constituent of O etc. trace, but these gaseous constituents are difficult to only by burning till fully of coating layer, remove, and result, when the laser sealing-in, with CO
2gas, H
2the form of O gas is discarded to outside.If these gases that are released contact with organic EL, promote the deteriorated of organic EL, the long-term reliability of organic EL device reduces.In order to suppress this problem, although the method that the material of adsorbed gas composition is set in the inside of organic EL device is arranged, there is the shortcoming that causes manufacturing cost to raise.
Therefore, the 2nd technical task of the present invention is, initiates out when the laser sealing-in, be difficult to emit from the seal, sealing materials layer method of gaseous constituent, thus, the material of adsorbed gas composition is set even without the inside at organic EL device etc., also can improves the long-term reliability of organic EL device etc.
For solving the method for problem
The<the 1 invention >
The result of people's further investigation of the present invention is, discovery is by being used the seal, sealing materials that at least comprises inorganic powder, the content of the resistivity against fire filler in inorganic powder is limited in to specialized range, and the surface smoothness of raising seal, sealing materials layer, thereby can solve above-mentioned the 1st technical task, as the 1st invention, propose following scheme.; glass substrate with the seal, sealing materials layer of the present invention; it is characterized in that; it possesses the seal, sealing materials layer made after the seal, sealing materials sintering; wherein, seal, sealing materials at least comprises inorganic powder, and inorganic powder comprises glass powder and resistivity against fire filler; the content of the resistivity against fire filler in inorganic powder is 10 volume %～35 volume %, and the surface roughness Ra of seal, sealing materials layer is less than 0.5 μ m.At this, " inorganic powder " refers to the inorganic materials powder beyond pigment, usually, refers to the mixture of glass powder and resistivity against fire filler." surface roughness Ra " refers to the value (following same) determined according to the method for JIS B0601:2001.It should be noted that, as glass powder, can use various glass powders, but as described later, preferably contain the glass powder of SnO or contain Bi
2o
3glass powder.
In the seal, sealing materials of the 1st invention, inorganic powder comprises glass powder and resistivity against fire filler, and the content of the resistivity against fire filler in inorganic powder is 10～35 volume %.If more than the content of resistivity against fire filler is limited in to 10 volume %, can makes the thermal expansivity of seal, sealing materials layer reduce, and can improve the physical strength of seal, sealing materials layer.In addition, if the content of resistivity against fire filler is limited in below 35 volume %, be difficult to hinder the softening mobility of seal, sealing materials, easily improve the surface smoothness of seal, sealing materials layer.
The surface roughness Ra of the seal, sealing materials layer of the 1st invention is less than 0.5 μ m.Thus, glass substrate adaptation each other improves, and the laser sealing-in significantly improves.
Second, the glass substrate with the seal, sealing materials layer of the 1st invention, it possesses the seal, sealing materials layer made after the seal, sealing materials sintering, it is characterized in that, described seal, sealing materials comprises inorganic powder and pigment, described inorganic powder comprises glass powder and resistivity against fire filler, and the content of the resistivity against fire filler in described inorganic powder is 10～35 volume %, and the surfaceness RMS of described seal, sealing materials layer is less than 1.0 μ m.At this, " surfaceness RMS " adopts the value (following same) determined according to the method for JIS B0601:2001.
The 3rd, preferably: in the glass substrate with the seal, sealing materials layer of the 1st invention, the mean thickness of described seal, sealing materials layer is less than 10 μ m.
The 4th, preferably: in the glass substrate with the seal, sealing materials layer of the 1st invention, does not grind on the surface of described seal, sealing materials layer.
The 5th, preferably: in the glass substrate with the seal, sealing materials layer of the 1st invention, described glass powder is the glass powder that contains SnO.Thus, due to the softening temperature reduction of glass powder, so the softening temperature of seal, sealing materials also reduces.Consequently, the laser sealing-in finishes at short notice, and can when the laser sealing-in, improve sealing strength.At this, " glass powder that contains SnO " refers to, as the glass composition, comprises the SnO (following same) more than 20 % by mole.
The 6th, preferably: in the glass substrate with the seal, sealing materials layer of the 1st invention, glass powder forms in following oxide compound and converts and contain 35%～70% SnO, 10%～30% P as glass
2o
5.Thus, can maintain the low melting point characteristic of glass, and easily improve the water tolerance of glass.At this, " following oxide compound conversion " refers to: for example, in the situation that stannic oxide, even the stannic oxide (SnO of tetravalence
2), also be scaled the stannic oxide (SnO) of divalence, and explain with the form of " SnO "; In addition, for example, in the situation that ferric oxide, even the ferric oxide of divalence (FeO) also is scaled the ferric oxide (Fe of trivalent
2o
3), and with " Fe
2o
3" form statement (following same).
The 7th, preferably: in the glass substrate with the seal, sealing materials layer of the 1st invention, described glass powder is for containing Bi
2o
3glass powder.Thus, the softening temperature of glass powder reduces, and the softening temperature of seal, sealing materials also reduces.In addition, owing to containing Bi
2o
3glass powder excellence aspect water tolerance, sealing strength, therefore can make at short notice the laser sealing-in finish, can guarantee for a long time sealing strength in addition.At this, " contain Bi
2o
3glass powder " refer to, form and comprise the Bi more than 20 % by mole as glass
2o
3(following same).
The 8th, preferably: in the glass substrate with the seal, sealing materials layer of the 1st invention, glass powder forms in following oxide compound and converts and contain 20%～60% Bi as glass
2o
3, 10%～35% B
2o
3, 5%～40% ZnO, 5%～30% CuO+Fe
2o
3.Thus, can maintain the low melting point characteristic of glass, and easily improve the water tolerance of glass.And, easily improve sealing strength.At this, " CuO+Fe
2o
3" refer to CuO and Fe
2o
3total amount.
The 9th, preferably: in the glass substrate with the seal, sealing materials layer of the 1st invention, the median size D of resistivity against fire filler
50be below 5 μ m.Thus, because the surface smoothness of seal, sealing materials layer improves, therefore easily laser is converted to heat energy, thus easily hanging down output rating, at a high speed by the glass substrate laser sealing-in, and easily make narrow and smallization of thickness of seal, sealing materials layer.At this, " median size D
50" referring to the value of measuring by laser diffractometry, in the cumulative grain-size distribution curve of the volume reference while meaning to measure by laser diffractometry, the side that its semi-invariant is little from particle starts to accumulate and is 50% particle diameter.In addition similarly, " maximum particle diameter D described later
99" referring to the value of measuring by laser diffractometry, in the cumulative grain-size distribution curve of the volume reference while meaning to measure by laser diffractometry, the side that its semi-invariant is little from particle starts to accumulate and is 99% particle diameter.In addition similarly, " 90% particle diameter D described later
90" refer to the value of measuring by laser diffractometry, mean to measure by laser diffractometry in the cumulative grain-size distribution curve of volume reference, the side that its semi-invariant is little from particle starts to accumulate and is 90% particle diameter.It should be noted that, with these " median size D
50", " maximum particle diameter D
99", and " 90% particle diameter D
90" relevant item, following also identical.
The tenth, preferably: in the glass substrate with the seal, sealing materials layer of the 1st invention, the maximum particle diameter D of described resistivity against fire filler
99be less than 10 μ m.Thus, because the surface smoothness of seal, sealing materials layer improves, therefore easily laser is converted to heat energy, thus easily hanging down output rating, at a high speed by the glass substrate laser sealing-in, and easily make narrow and smallization of thickness of seal, sealing materials layer.
The 11, preferably: in the glass substrate with the seal, sealing materials layer of the 1st invention, the resistivity against fire filler is for selecting white trichroite, zircon, stannic oxide, niobium oxides, zirconium phosphate system pottery, NbZr (PO
4)
3in one or more.
The 12, preferably: in the glass substrate with the seal, sealing materials layer of the 1st invention, described seal, sealing materials also comprises pigment, and this pigment optimization is carbon.Thus, by pigment, laser is converted into heat energy, therefore can improve the laser sealing-in.In addition, the excellent color reproducing performance of carbon, the absorptivity of laser is good.In addition, carbon also has following effect: the effect of the situation that the glass powder that prevents from containing SnO when the laser sealing-in is rotten, that is, while preventing the laser sealing-in, the SnO of glass in forming is oxidized to SnO
2the effect of situation.It should be noted that, as carbon, can use various materials, but amorphous carbon or graphite are suitable especially.
The 13, preferably: in the glass substrate with the seal, sealing materials layer of the 1st invention, the content of the pigment in described seal, sealing materials is 0.2～0.7 quality %.If more than the content of pigment is defined as to 0.2 quality %, therefore easily laser can be converted to heat energy efficiently, only part that should sealing-in be carried out to local heating, consequently, can prevent the thermal degradation when of active component etc., and easily by glass substrate laser sealing-in each other.On the other hand, if the content of pigment is limited in below 1 quality %, the superheated in the time of can suppressing laser radiation, and, when the laser sealing-in, easily prevent the situation of glass generation devitrification.
The 14, preferably: the glass substrate with the seal, sealing materials layer of the 1st invention is for the sealing-in of organic EL device.At this, " organic EL device " comprises OLED display, organic EL illuminating etc. (following same).
The 15, preferably: the glass substrate with the seal, sealing materials layer of the 1st invention is for the laser sealing-in.It should be noted that, as mentioned above, if adopt the laser sealing-in, can be only part that should sealing-in be carried out to local heating, therefore can prevent the thermal degradation when of active component etc., and glass substrate can be carried out to sealing-in each other.
The laser sealing-in can be used various laser.Particularly, consider preferred semiconductor laser, YAG laser, CO from the aspect of easy handling
2laser, excimer laser, infrared laser etc. (following same).
The 16, preferably: the glass substrate with the seal, sealing materials layer of the 1st invention is for the laser sealing-in under inert atmosphere.At this, " inert atmosphere " comprises the reduced atmosphere such as neutral gas atmosphere, vacuum atmosphere such as N2 gas atmosphere, Ar gas atmosphere (following same).
The organic EL device of the 17,1st invention, is characterized in that, of the above-mentioned glass substrate with the seal, sealing materials layer, makes.
The<the 2 invention >
The result that the present invention further investigate is, finds by the laser sealing temperature is limited in below the firing temperature of coating layer, thereby can solve above-mentioned the 2nd technical task, as the 2nd invention, proposes following scheme.That is, the manufacture method of the electron device of the 2nd invention, it manufactures electron device by the laser sealing-in, it is characterized in that, comprises following operation: (1) prepares the operation of glass substrate; (2) material containing that will comprise the seal, sealing materials of glass powder and comprise organic binder bond mixes, and makes the operation of seal, sealing materials paste; (3) operation of the described seal, sealing materials paste formation of coating coating layer on described glass substrate; (4) described coating layer is burnt till, obtained the operation with the glass substrate of seal, sealing materials layer; (5) across described seal, sealing materials layer, the operation that the described glass substrate with the seal, sealing materials layer is overlapped with the glass substrate that does not form the seal, sealing materials layer; And (6) reach the mode irradiating laser below firing temperature with the laser sealing temperature, make the described glass substrate with the seal, sealing materials layer and do not form the operation of the glass substrate hermetic seal of described seal, sealing materials layer.At this, in the situation that " burning till coating layer ", both can make to burn the operation (unsticking mixture operation) of removing the organic binder bond that coating layer comprises and separate with the operation (sintering circuit) of sinter coating layer, also can carry out simultaneously." do not form the glass substrate of seal, sealing materials layer " and typically refer to the glass substrate of the original paper that is formed with electron device." laser sealing temperature " used radiation thermometer to measure the temperature of seal, sealing materials layer and the value that obtains while referring to the laser sealing-in." firing temperature ", in the operation of above-mentioned (4) that coating layer is burnt till, refers to the top temperature in operation; Separate with the operation of sinter coating layer in the situation that make to burn the operation remove the organic binder bond that coating layer comprises, refer to the top temperature of arbitrary operation.
The viscosity of gas discharging amount and seal, sealing materials is inversely proportional to.If improve the firing temperature of coating layer, the reduced viscosity of seal, sealing materials, although the gas discharging amount increases, at this, the gas of emitting can not make organic EL deteriorated.In addition, if the laser sealing temperature is reduced, the viscosity rise of seal, sealing materials, the gas discharging amount reduces.Therefore, if the laser sealing temperature is limited in below firing temperature, can when the laser sealing-in, suppress significantly the gas discharging amount.As the laser sealing temperature is limited in to the method below firing temperature, there is the method that improves firing temperature or reduce the laser sealing temperature.In the situation that the former method, it is effective selecting the method for the glass system that thermostability is high.In the situation that the latter's method, the method for optimizing the illuminate condition of laser is effectively, and the method for content of optimizing in addition the absorption composition of the laser in seal, sealing materials is also effective.
The second, preferably: in the manufacture method of the electron device of the 2nd invention, described laser sealing temperature is below 500 ℃.Thus, when the laser sealing-in, emit gas volume and tail off.
The 3rd, preferably: in the manufacture method of the electron device of the 2nd invention, the inorganic powder that comprises glass powder that described seal, sealing materials contains 97.5 quality %～100 quality % and the pigment of 0 quality %～2.5 quality %.Thus, the resistance to air loss of OLED display inside can be guaranteed by the laser sealing-in, therefore the H that makes organic luminous layer deteriorated can be prevented
2o, O
2invade the situation of OLED display inside, result is to improve the long-term reliability of OLED display.
If the content of inorganic powder is less than 97.5 quality %, during the laser sealing-in, seal, sealing materials lacks softening mobility, and is difficult to improve sealing strength.It should be noted that, if more than the content of pigment is limited in to 0.05 quality %, can efficiently laser be converted to heat energy, therefore easily only part that should sealing-in is carried out to local heating, result is the thermal degradation when that can prevent active component etc., and easily glass substrate is carried out to the laser sealing-in each other.On the other hand, if the content of pigment is limited in below 2.5 quality %, during the laser sealing-in, thereby rising undeservedly, the temperature that can prevent the seal, sealing materials layer emits the many situations of gas quantitative change.And, easily prevent the situation of glass generation devitrification.
The 4th, preferably: in the manufacture method of the electron device of the 2nd invention, described glass powder as glass form in following oxide compound, convert % by mole, contain 35%～70% SnO, 10%～30% P
2o
5.Thus, the softening temperature of glass powder reduces, so the softening temperature of seal, sealing materials also reduces.Consequently the laser sealing-in finishes at short notice, and can when the laser sealing-in, improve sealing strength.
The 5th, preferably: in the manufacture method of the electron device of the 2nd invention, described glass powder as glass form in following oxide compound, convert % by mole, contain 20%～60% Bi
2o
3, 10%～35% B
2o
3, 5%～40% ZnO, 5%～30% CuO+Fe
2o
3.Thus, the softening temperature of glass powder reduces, so the softening temperature of seal, sealing materials also reduces.And, when the laser sealing-in, thereby the energy of irradiated laser directly can be absorbed and be converted to efficiently heat, and can promote reacting of seal, sealing materials and glass substrate.Consequently, the laser sealing-in finishes at short notice, and can when the laser sealing-in, improve sealing strength.
The 6th, preferably: in the manufacture method of the electron device of the 2nd invention, described pigment is for selecting white C (carbon), Co
3o
4, CuO, Cr
2o
3, Fe
2o
3, MnO
2, SnO, Ti
no
2n-1one or more in (n is integer), spinel system complex oxide.
The 7th, preferably: in the manufacture method of the electron device of the 2nd invention, described inorganic powder also comprises the resistivity against fire filler of 0.1 volume %～60 volume %.
The 8th, preferably: in the manufacture method of the electron device of the 2nd invention, described electron device is organic EL device.
The 9th, preferably: in the manufacture method of the electron device of the 2nd invention, described organic binder bond is aliphatic poly ethylene series carbonic ether.
The tenth, preferably: in the manufacture method of the electron device of the 2nd invention, carry out burning till of described coating layer under inert atmosphere.
The electron device of the 11,2nd invention is characterized in that its manufacture method by above-mentioned electron device is made.
The<the 1 related invention >
The result of people's further investigation of the present invention is; discovery is after producing stacked film by multiple seal, sealing materials paste; burnt till and formed the seal, sealing materials layer; and the granularity micronize of the glass powder that the outermost layer that makes this stacked film comprises; can solve thus above-mentioned the 1st technical task, as the 1st related invention, propose following scheme.That is, the manufacture method of the glass substrate with the seal, sealing materials layer of the 1st related invention, is characterized in that, has following operation: the operation of preparing glass substrate; Be coated with the first seal, sealing materials paste on described glass substrate, then form the operation of the first seal, sealing materials film; Be coated with the second seal, sealing materials paste on described the first seal, sealing materials film, then form the operation of the second seal, sealing materials film; Burnt till with the stacked film to gained, formed the operation of seal, sealing materials layer on described glass substrate; And described the first seal, sealing materials paste comprises the first glass powder, and described the second seal, sealing materials paste comprises the second glass powder, the median size D of described the second glass powder
50be less than the median size D of described the first glass powder
50.At this, " the second seal, sealing materials film " forms single layer usually, becomes the outermost layer of seal, sealing materials film, if but the material formation is identical, and also can a plurality of layers.In addition, " the first seal, sealing materials film " refers to the seal, sealing materials film except the second seal, sealing materials film, usually, refer to the outermost layer layer in addition of seal, sealing materials film, but be not defined as single layer, also comprise the situation of a plurality of layers, in this case, the material formation also can be different." the first seal, sealing materials film " and " the second seal, sealing materials film " is not only the desciccator diaphragm after the solvent evaporates made in material containing, also comprises the remaining wet film that solvent in material containing is arranged.It should be noted that, the item relevant with " the second seal, sealing materials film " with these " first seal, sealing materials films " is following identical.As glass powder, can use various glass powders, but as described later, preferably contain the glass powder of SnO or contain Bi
2o
3glass powder.
People of the present invention notice if improve the seal, sealing materials layer with by the sealing-in thing (for example, be formed with the glass substrate of element) adaptation, can use the laser of low output rating to carry out the laser sealing-in, therefore find that the surface smoothness of raising seal, sealing materials layer is very important.And; people of the present invention find, if the granularity that makes the glass powder in the size ratio first seal, sealing materials film of the glass powder in the second seal, sealing materials film micronize is more burnt till stacked film; form in the situation of seal, sealing materials layer, the surface smoothness of seal, sealing materials layer significantly improves.
Therefore, the glass substrate with the seal, sealing materials layer of the 1st related invention, can use the laser of low output rating to carry out the laser sealing-in.In addition, owing to can suitably guaranteeing the resistance to air loss of organic EL device inside, therefore can prevent the H that makes organic luminous layer deteriorated
2o, O
2deng the situation of invading organic EL device inside.Result is to improve the long-term reliability of organic EL device.It should be noted that, in the present invention, can utilize the second seal, sealing materials film to guarantee the surface smoothness of seal, sealing materials layer.Result, with respect to the glass powder in the first seal, sealing materials film, does not need excessive micronize, can form at an easy rate the seal, sealing materials layer.
The manufacture method of the glass substrate with the seal, sealing materials layer of the second, the 1 related invention, is characterized in that, has following operation: the operation of preparing glass substrate; After coating the first seal, sealing materials paste, form the operation of the first seal, sealing materials film on described glass substrate; After coating the second seal, sealing materials paste, form the operation of the second seal, sealing materials film on described the first seal, sealing materials film; Stacked film to gained is burnt till, and forms the operation of seal, sealing materials layer on described glass substrate; And described the first seal, sealing materials paste comprises the first glass powder, and described the second seal, sealing materials paste comprises the second glass powder, the maximum particle diameter D of described the second glass powder
99be less than the maximum particle diameter D of described the first glass powder
99.
The 3rd, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 1st related invention, the median size D of described the second glass powder
50be 0.1～2.0 μ m, and the median size D of described the first glass powder
50be 1.0～3.5 μ m.
The 4th, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 1st related invention, the maximum particle diameter D of described the second glass powder
99be 0.5～6.1 μ m, and the maximum particle diameter D of described the first glass powder
99be 3.0～15.0 μ m.
The 5th, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 1st related invention, the glass of described the first glass powder forms with the glass composition of described the second glass powder roughly the same.At this, the content that " glass form roughly the same " refers to each composition of glass in forming for ± 3 % by mole with interior situation.
The 6th, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 1st related invention, described the first glass powder and described the second glass powder are the glass powder that contains SnO.Thus, due to the softening temperature reduction of glass powder, so the softening temperature of seal, sealing materials also reduces.Consequently, the laser sealing-in completes at short notice, and can when the laser sealing-in, improve sealing strength.
The 7th, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 1st related invention, the glass that the described glass powder that contains SnO converts as following oxide compound forms, and in mol%, contains 35%～70% SnO, 10%～30% P
2o
5.Thus, on the basis of the low melting point characteristic that has maintained glass, also easily improve the water tolerance of glass.
The 8th, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 1st related invention, described the first glass powder and described the second glass powder are for containing Bi
2o
3glass powder.Thus, the softening temperature of glass powder reduces, and the softening temperature of seal, sealing materials also reduces.Consequently, the laser sealing-in completes at short notice, and can when the laser sealing-in, improve sealing strength.
The 9th, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 1st related invention, the described Bi that contains
2o
3the glass that converts as following oxide compound of glass powder form, in mol%, contain 20%～60% Bi
2o
3, 10%～35% B
2o
3, 5%～40% ZnO, 5%～30% CuO+Fe
2o
3.Thus, due to the softening temperature reduction of glass powder, so the softening temperature of seal, sealing materials also reduces.And, during the laser sealing-in, thereby the energy of irradiated laser directly can be absorbed and is converted to efficiently heat, and can promote reacting of seal, sealing materials and glass substrate.Consequently, the laser sealing-in completes at short notice, and can when the laser sealing-in, improve sealing strength.
The tenth, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 1st related invention, described the first seal, sealing materials paste and described the second seal, sealing materials paste also comprise the resistivity against fire filler.Thus, the physical strength of seal, sealing materials layer easily improves, and the thermal expansivity of seal, sealing materials layer easily reduces.
The 11, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 1st related invention, described the first seal, sealing materials paste and described the second seal, sealing materials paste also comprise pigment.Thus, the easy absorbing laser of seal, sealing materials layer.
The 12, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 1st related invention, described pigment is carbon.
The 13, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 1st related invention, the surface roughness Ra of described seal, sealing materials layer is below 0.6 μ m.
The 14, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 1st related invention, the surfaceness RMS of described seal, sealing materials layer is below 1.0 μ m.
The 15, preferably: the glass substrate with the seal, sealing materials layer of the 1st related invention, it is characterized in that, its manufacture method by the above-mentioned glass substrate with the seal, sealing materials layer is made.
The 16, the manufacture method of the electron device of the 1st related invention, it is characterized in that, it will manufacture electron device with the glass substrate of seal, sealing materials layer and the glass substrate sealing-in that does not form the seal, sealing materials layer, wherein, manufacture the described glass substrate with the seal, sealing materials layer by above-mentioned method, and to described seal, sealing materials layer irradiating laser, thereby by the described glass substrate with the seal, sealing materials layer with do not form the glass substrate sealing-in of described seal, sealing materials layer.It should be noted that, as mentioned above, by the laser sealing-in, can be only part that should sealing-in be carried out to local heating, therefore can prevent the thermal degradation when of active component etc., and by glass substrate sealing-in each other.
The 17, preferably: in the manufacture method of the electron device of the 1st related invention, described electron device is organic EL device.
The seal, sealing materials of the 18,1st related invention, is characterized in that, its seal, sealing materials at least comprising glass powder, the median size D of glass powder
50be 0.1～2.0 μ m, described seal, sealing materials is for the formation of seal, sealing materials layer.
The seal, sealing materials of the 19,1st related invention, is characterized in that, its seal, sealing materials at least comprising glass powder, the maximum particle diameter D of glass powder
99be 0.5～6.1 μ m, described seal, sealing materials is for the formation of seal, sealing materials layer.
The 20, preferably: with regard to the seal, sealing materials of the 1st related invention, the surface roughness Ra of described seal, sealing materials layer is 0.6 μ m.
The 21, preferably: with regard to the seal, sealing materials of the 1st related invention, the surfaceness RMS of described seal, sealing materials layer is below 1.0 μ m.
The<the 2 related invention >
The result of people's further investigation of the present invention is, discovery is after producing stacked film by multiple seal, sealing materials paste, burnt till and formed the seal, sealing materials layer, and the softening temperature low temperature of the glass powder that the outermost layer that makes this stacked film comprises, can solve thus above-mentioned the 1st technical task, as the 2nd related invention, propose following scheme.That is, the manufacture method of the glass substrate with the seal, sealing materials layer of the 2nd related invention, is characterized in that, it has following operation: the operation of preparing glass substrate; Be coated with the first seal, sealing materials paste on described glass substrate, then form the operation of the first seal, sealing materials film; Be coated with the second seal, sealing materials paste on described the first seal, sealing materials film, then form the operation of the second seal, sealing materials film; Stacked film to gained is burnt till, and forms the operation of seal, sealing materials layer on described glass substrate; And described the first seal, sealing materials paste comprises the first glass powder, and described the second seal, sealing materials paste comprises the second glass powder, and the softening temperature of described the second glass powder is lower than the softening temperature of described the first glass powder.At this, " softening temperature " refers to the value of using large-scale differential thermal analysis (DTA) device to measure, and DTA starts to measure from room temperature, and heat-up rate is made as 10 ℃/minute.For example,, in the situation that the glass powder that use contains SnO, as long as measure under nitrogen atmosphere, contains Bi in use
2o
3the situation of glass powder under, as long as measure under air atmosphere.And the softening temperature that uses large-scale DTA device to measure refers to the temperature (Ts) of the 4th flex point shown in Fig. 1.It should be noted that, about these item, below also identical.As glass powder, can use various glass powders, but preferably contain the glass powder of SnO or contain Bi
2o
3glass powder.
People of the present invention notice if improve the seal, sealing materials layer with by the sealing-in thing (for example, be formed with the glass substrate of element) adaptation, can use the laser of low output rating to carry out the laser sealing-in, therefore find that the surface smoothness of raising seal, sealing materials layer is very important.And, people of the present invention find, if make the softening temperature of the softening temperature of the glass powder in the second seal, sealing materials film lower than the glass powder in the first seal, sealing materials film, stacked film to be burnt till and formed in the situation of seal, sealing materials layer, the surface smoothness of seal, sealing materials layer significantly improves.
Therefore, the glass substrate with the seal, sealing materials layer of the 2nd related invention, can use the laser of low output rating to carry out the laser sealing-in.In addition, owing to can suitably guaranteeing the resistance to air loss of organic EL device inside, therefore can prevent the H that makes organic luminous layer deteriorated
2o, O
2deng the situation of invading organic EL device inside.Result is to improve the long-term reliability of organic EL device.It should be noted that, in the 2nd related invention, can utilize the second seal, sealing materials film to guarantee the surface smoothness of seal, sealing materials layer.As a result, with respect to the glass powder in the first seal, sealing materials film, do not need excessive eutectic to reveal, in the situation that with the seal, sealing materials layer on the whole, can improve the thermostability of seal, sealing materials layer.
The second, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 2nd related invention, the value of (density of the density of described the second glass powder-described the first glass powder) is 0.01～0.50g/cm
3.
The 3rd, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 2nd related invention, the value of (thermal expansivity of the thermal expansivity of described the second glass powder-described the first glass powder) is 0.5 * 10
-7～10 * 10
-7/ ℃.At this, " thermal expansivity " is the mean value that utilizes push-down MEASURING THE THERMAL EXPANSION COEFFICIENT (TMA) device to measure, and for example at the glass powder that contains SnO, (comprises SnO-P
2o
5the glass frit end) in situation, refer to the mean value of measuring the temperature range of 30 ℃～250 ℃, for example containing Bi
2o
3glass powder (Bi
2o
3-B
2o
3the glass frit end), in situation, refer to the mean value of measuring the temperature range of 30 ℃～300 ℃.As measuring sample, for example, can use sintered compact is processed as to the sample after predetermined shape.It should be noted that, the item relevant to these thermal expansivity, following identical.
The 4th, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 2nd related invention, described the first glass powder and described the second glass powder are the glass powder that contains SnO.Thus, due to the softening temperature reduction of glass powder, so the softening temperature of seal, sealing materials also reduces.Consequently, the laser sealing-in completes at short notice, and can when the laser sealing-in, improve sealing strength.
The 5th, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 2nd related invention, the glass that the described glass powder that contains SnO converts as following oxide compound forms, and in mol%, contains 35%～70% SnO, 10%～30% P
2o
5.Thus, on the basis of the low melting point characteristic that has maintained glass, also easily improve the water tolerance of glass.
The 6th, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 2nd related invention, described the first glass powder and described the second glass powder are for containing Bi
2o
3glass powder.Thus, the softening temperature of glass powder reduces, and the softening temperature of seal, sealing materials also reduces.Consequently, the laser sealing-in completes at short notice, and can when the laser sealing-in, improve sealing strength.
The 7th, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 2nd related invention, the described Bi that contains
2o
3the glass that converts as following oxide compound of glass powder form, in mol%, contain 20%～60% Bi
2o
3, 10%～35% B
2o
3, 5%～40% ZnO, 5%～30% CuO+Fe
2o
3.Thus, due to the softening temperature reduction of glass powder, so the softening temperature of seal, sealing materials also reduces.And, during the laser sealing-in, the energy of irradiated laser directly can be absorbed, thereby be converted to heat efficiently, and can promote reacting of seal, sealing materials and glass substrate.Consequently, the laser sealing-in completes at short notice, and can when the laser sealing-in, improve sealing strength.
The 8th, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 2nd related invention, described the first seal, sealing materials paste and described the second seal, sealing materials paste also comprise the resistivity against fire filler.Thus, the physical strength of seal, sealing materials layer easily improves, and the thermal expansivity of seal, sealing materials layer easily reduces.
The 9th, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 2nd related invention, described the first seal, sealing materials paste and described the second seal, sealing materials paste also comprise pigment.Thus, the easy absorbing laser of seal, sealing materials layer.
The tenth, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 2nd related invention, described pigment is carbon.The excellent color reproducing performance of carbon, the absorptivity of extinction is good.In addition, carbon also has following effect: the effect of the situation that the glass powder that prevents from containing SnO when the laser sealing-in is rotten, that is, while preventing the laser sealing-in, the SnO of glass in forming is oxidized to SnO
2the effect of situation.It should be noted that, as carbon, can use various materials, but amorphous carbon or graphite are particularly suitable for.
The 11, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 2nd related invention, the surface roughness Ra of described seal, sealing materials layer is below 0.6 μ m.
The 12, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 2nd related invention, the surfaceness RMS of described seal, sealing materials layer is below 1.0 μ m.
The 13, the manufacture method of the electron device of the 2nd related invention, it is characterized in that, to manufacture electron device with the glass substrate of seal, sealing materials layer and the glass substrate sealing-in that does not form the seal, sealing materials layer, wherein, manufacture the described glass substrate with the seal, sealing materials layer by above-mentioned method, and to described seal, sealing materials layer irradiating laser, thereby by the described glass substrate with the seal, sealing materials layer with do not form the glass substrate sealing-in of described seal, sealing materials layer.It should be noted that, as mentioned above, by the laser sealing-in, can be only part that should sealing-in be carried out to local heating, therefore can prevent the thermal degradation when of active component etc., and by glass substrate sealing-in each other.
The 14, preferably: in the manufacture method of the electron device of the 2nd related invention, described electron device is organic EL device.
The glass substrate with the seal, sealing materials layer of the 15,2nd related invention, is characterized in that, its manufacture method by the above-mentioned glass substrate with the seal, sealing materials layer is made.
The 16, the glass substrate with the seal, sealing materials layer of the 2nd related invention, it is characterized in that, it is coated with after the seal, sealing materials paste to be burnt till and forms on glass substrate, wherein, with comparing with the contact area of described glass substrate in described seal, sealing materials layer, in described seal, sealing materials layer more softening with contact area by the sealing-in thing.
The seal, sealing materials of the 17,2nd related invention, is characterized in that, its seal, sealing materials at least comprising glass powder, and the softening temperature of glass powder is below 400 ℃, described seal, sealing materials is for the formation of seal, sealing materials layer.
The<the 3 related invention >
The result of people's further investigation of the present invention is, discovery is after producing stacked film by multiple seal, sealing materials paste, burnt till and formed the seal, sealing materials layer, and the content of the resistivity against fire filler that the outermost layer that makes this stacked film comprises reduces, can solve thus above-mentioned the 1st technical task, as the 3rd related invention, propose following scheme.That is, the manufacture method of the glass substrate with the seal, sealing materials layer of the 3rd related invention, is characterized in that, has following operation: the operation of preparing glass substrate; Be coated with the first seal, sealing materials paste on described glass substrate, then form the operation of the first seal, sealing materials film; Be coated with the second seal, sealing materials paste on described the first seal, sealing materials film, then form the operation of the second seal, sealing materials film; Stacked film to gained is burnt till, and forms the operation of seal, sealing materials layer on described glass substrate; And described the first seal, sealing materials paste comprises the first seal, sealing materials, and described the second seal, sealing materials paste comprises the second seal, sealing materials, and the content of the resistivity against fire filler in described the second seal, sealing materials is less than the content of the resistivity against fire filler in described the first seal, sealing materials.At this, " the first seal, sealing materials " refers to the material of removing from the first seal, sealing materials paste after the material containing composition, particularly, refers to when making the first seal, sealing materials paste, to be ready adding the material before material containing." the second seal, sealing materials " refers to the material of removing from the second seal, sealing materials paste after the material containing composition, particularly, refers to when making the second seal, sealing materials paste, to be ready adding the material before material containing.It should be noted that, the item relevant with " the second seal, sealing materials " to these " first seal, sealing materials ", following identical.
People of the present invention notice if improve the seal, sealing materials layer with by the sealing-in thing (for example, be formed with the glass substrate of element) adaptation, can use the laser of low output rating to carry out the laser sealing-in, therefore find that the surface smoothness of raising seal, sealing materials layer is very important.And, people of the present invention find, if make the content of the resistivity against fire filler in the second seal, sealing materials be less than the content of the resistivity against fire filler in the first seal, sealing materials, stacked film are burnt till, form in the situation of seal, sealing materials layer, the surface smoothness of seal, sealing materials layer significantly improves.And, people of the present invention find, if make the content of the resistivity against fire filler in the second seal, sealing materials be less than the content of the resistivity against fire filler in the first seal, sealing materials, stacked film are burnt till, form in the situation of seal, sealing materials layer, be difficult to remaining irrational stress in the seal, sealing materials layer.
Therefore, the glass substrate with the seal, sealing materials layer of the 3rd related invention, can use the laser of low output rating to carry out the laser sealing-in.In addition, owing to can suitably guaranteeing the resistance to air loss of organic EL device inside, therefore can prevent the H that makes organic luminous layer deteriorated
2o, O
2deng the situation of invading organic EL device inside.Result is to improve the long-term reliability of organic EL device.
And, as long as add the resistivity against fire filler in the first seal, sealing materials and the second seal, sealing materials, the physical strength of seal, sealing materials layer easily improves, and the thermal expansivity of seal, sealing materials layer easily reduces.
Second, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 3rd related invention, the content of the resistivity against fire filler in described the second seal, sealing materials (wherein, remove the content of pigment and calculate) be 5 volume %～40 volume %, and the content of the resistivity against fire filler in described the first seal, sealing materials (wherein, remove the content of pigment and calculate) is 20 volume %～60 volume %.
The 3rd, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 3rd related invention, the value of (thermal expansivity of the thermal expansivity of described the second seal, sealing materials-described the first seal, sealing materials) is 1 * 10
-7～45 * 10
-7/ ℃.
The 4th, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 3rd related invention, described the first seal, sealing materials and described the second seal, sealing materials also comprise the glass powder that contains SnO.Thus, due to the softening temperature reduction of glass powder, so the softening temperature of seal, sealing materials also reduces.Consequently, the laser sealing-in completes at short notice, and can when the laser sealing-in, improve sealing strength.
The 5th, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 3rd related invention, the glass that the described glass powder that contains SnO converts as following oxide compound forms, and in mol%, contains 35%～70% SnO, 10%～30% P
2o
5.Thus, on the basis of the low melting point characteristic that has maintained glass, also easily improve the water tolerance of glass.
The 6th, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 3rd related invention, described the first seal, sealing materials and described the second seal, sealing materials also comprise and contain Bi
2o
3glass powder.Thus, the softening temperature of glass powder reduces, and the softening temperature of seal, sealing materials also reduces.Consequently, the laser sealing-in completes at short notice, and can when the laser sealing-in, improve sealing strength.
The 7th, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 3rd related invention, the described Bi that contains
2o
3the glass that converts as following oxide compound of glass powder form, in mol%, contain 20%～60% Bi
2o
3, 10%～35% B
2o
3, 5%～40% ZnO, 5%～30% CuO+Fe
2o
3.Thus, the softening temperature of glass powder reduces, so the softening temperature of seal, sealing materials also reduces.And, when the laser sealing-in, the energy of irradiated laser directly can be absorbed, thereby be converted to heat efficiently, and can promote reacting of seal, sealing materials and glass substrate.Consequently, the laser sealing-in completes at short notice, and can when the laser sealing-in, improve sealing strength.
The 8th, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 3rd related invention, described the first seal, sealing materials and described the second seal, sealing materials also comprise pigment.Thus, the easy absorbing laser of seal, sealing materials layer.
The 9th, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 3rd related invention, described pigment is carbon.
The tenth, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 3rd related invention, the surface roughness Ra of described seal, sealing materials layer is below 0.6 μ m.
The 11, preferably: in the manufacture method of the glass substrate with the seal, sealing materials layer of the 3rd related invention, the surfaceness RMS of described seal, sealing materials layer is below 1.0 μ m.
The 12, preferably: the manufacture method of the electron device of the 3rd related invention, it is characterized in that, it will manufacture electron device with the glass substrate of seal, sealing materials layer and the glass substrate sealing-in that does not form the seal, sealing materials layer, wherein, manufacture the described glass substrate with the seal, sealing materials layer by above-mentioned method, and to described seal, sealing materials layer irradiating laser, by the described glass substrate with the seal, sealing materials layer with do not form the glass substrate sealing-in of described seal, sealing materials layer.It should be noted that, as mentioned above, by the laser sealing-in, can be only part that should sealing-in be carried out to local heating, therefore can prevent the thermal degradation when of active component etc., and by glass substrate sealing-in each other.
The 13, preferably: in the manufacture method of the electron device of the 3rd related invention, described electron device is organic EL device.
The glass substrate with the seal, sealing materials layer of the 14,3rd related invention, is characterized in that, its manufacture method by the above-mentioned glass substrate with the seal, sealing materials layer is made.
The 15, the glass substrate with the seal, sealing materials layer of the 3rd related invention, it is characterized in that, it is burnt till and is formed after glass substrate coating seal, sealing materials paste, wherein, described seal, sealing materials layer comprises glass powder and resistivity against fire filler, with regard to the content of described resistivity against fire filler, with the interior region of described seal, sealing materials layer, compare, the surf zone of described seal, sealing materials layer is less.
The 16, preferably: in the glass substrate with the seal, sealing materials layer of the 3rd related invention, the content of described resistivity against fire filler reduces gradually to interior region from the surf zone of described seal, sealing materials layer.
The accompanying drawing explanation
Fig. 1 means the schematic diagram of the softening temperature Ts of the seal, sealing materials while using large-scale DTA device to measure.
Fig. 2 A is the figure that the example for the manufacture method of the glass substrate to the seal, sealing materials layer describes, and means on glass substrate after coating the first seal, sealing materials paste, formed the sectional skeleton diagram of the state of the first seal, sealing materials film.
Fig. 2 B is the figure that the example for the manufacture method of the glass substrate to the seal, sealing materials layer describes, and means on the first seal, sealing materials film after coating the second seal, sealing materials paste, formed the sectional skeleton diagram of the state of the second seal, sealing materials film.
Fig. 2 C is the figure that the example for the manufacture method of the glass substrate to the seal, sealing materials layer describes, and means the sectional skeleton diagram that the stacked film of gained has been burnt till, formed the state of seal, sealing materials layer on glass substrate.
Fig. 2 D is the figure that the example for the manufacture method of the glass substrate to the seal, sealing materials layer describes, and means the glass substrate that makes not form the seal, sealing materials layer contacts configuration with the glass substrate with the seal, sealing materials layer of gained after, adopts the laser sealing-in and produce the sectional skeleton diagram of the state of electron device.
Embodiment
The<the 1 working of an invention mode >
The glass substrate with the seal, sealing materials layer of the 1st working of an invention mode has the seal, sealing materials layer after seal, sealing materials is burnt till.This seal, sealing materials comprises the inorganic powder that contains glass powder and resistivity against fire filler.By comprising the resistivity against fire film, can make the thermal expansivity of seal, sealing materials layer reduce, and can improve the physical strength of seal, sealing materials layer.It is described that glass powder, resistivity against fire filler suitable is constructed as follows.
Glass powder is preferably the glass powder that contains SnO.The glass powder that contains SnO forms mole expression % converted in following oxide compound as glass, preferably contain 35%～70% SnO, 10%～30% P
2o
5.Show the reason that the glass compositing range is limited as described above.It should be noted that, in the explanation of following glass compositing range, except the situation of specified otherwise, % means to refer to % by mole.
SnO is the composition that the glass eutectic is revealed.Its content is 35%～70%, 40%～70%, particularly is preferably 50%～68%.It should be noted that, as long as the content of SnO is more than 50%, during the laser sealing-in, glass is softening flowing easily.If the content of SnO is less than 35%, the viscosity of glass becomes too high, is difficult to use desirable Laser output to carry out the laser sealing-in.On the other hand, if the content of SnO, more than 70%, is difficult to vitrifying.
P
2o
5being network former, is the composition that improves thermostability.Its content is 10%～30%, preferably 15%～27%, is particularly preferably 15%～25%.If P
2o
5content be less than 10%, the easy step-down of thermostability.On the other hand, if P
2o
5content more than 30%, weathering resistance reduces, and is difficult to guarantee the long-term reliability of organic EL device etc.
Beyond mentioned component, can also add following composition.
ZnO is intermidate oxide, and is the composition that makes stabilization.Its content is 0%～30%, preferably 1%～20%, is particularly preferably 1%～15%.If the content of ZnO is more than 30%, thermostability easily reduces.
B
2o
3be network former, and be the composition that makes stabilization.In addition, B
2o
3it is the composition that improves weathering resistance.Its content is 0%～20%, preferably 1%～20%, is particularly preferably 2%～15%.If B
2o
3content more than 20%, the viscosity of glass becomes too high, is difficult to use desirable Laser output to carry out the laser sealing-in.
Al
2o
3be intermidate oxide, and be the composition that makes stabilization.In addition, Al
2o
3it is the composition that thermal expansivity is reduced.Its content is 0%～10%, preferably 0.1%～10%, is particularly preferably 0.5%～5%.If Al
2o
3content more than 10%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable Laser output to carry out the laser sealing-in.
SiO
2be network former, and be the composition that makes stabilization.Its content is 0%～15%, is particularly preferably 0%～5%.If SiO
2content more than 15%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable Laser output to carry out the laser sealing-in.
In
2o
3be the composition that improves thermostability, its content is preferably 0%～5%.If In
2o
3content more than 5%, job order cost is surging.
Ta
2o
5be the composition that improves thermostability, its content is preferably 0%～5%.If Ta
2o
5content more than 5%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable Laser output to carry out the laser sealing-in.
La
2o
3being the composition that improves thermostability, is the composition that improves weathering resistance in addition.Its content is 0%～15%, preferably 0%～10%, is particularly preferably 0%～5%.If La
2o
3content more than 15%, job order cost is surging.
MoO
3be the composition that improves thermostability, its content is preferably 0%～5%.If MoO
3content more than 5%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable Laser output to carry out the laser sealing-in.
WO
3be the composition that improves thermostability, its content is preferably 0%～5%.If WO
3content more than 5%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable Laser output to carry out the laser sealing-in.
Li
2o is the composition that the glass eutectic is revealed, and its content is preferably 0%～5%.If Li
2the content of O is more than 5%, and thermostability easily reduces.
Na
2o is the composition that the glass eutectic is revealed, and its content is 0%～10%, is particularly preferably 0%～5%.If Na
2the content of O is more than 10%, and thermostability easily reduces.
K
2o is the composition that the glass eutectic is revealed, and its content is preferably 0%～5%.If K
2the content of O is more than 5%, and thermostability easily reduces.
MgO is the composition that improves thermostability, and its content is preferably 0%～15%.If the content of MgO is more than 15%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable Laser output to carry out the laser sealing-in.
BaO is the composition that improves thermostability, and its content is preferably 0%～10%.If the content of BaO is more than 10%, the one-tenth balance-dividing that glass forms suffers damage, on the contrary the easy devitrification of glass.
F2 is the composition that the glass eutectic is revealed, and its content is preferably 0%～5%.If the content of F2 is more than 5%, thermostability easily reduces.
If consider thermostability and low melting point characteristic, In
2o
3, Ta
2o
5, La
2o
3, MoO
3, WO
3, Li
2o, Na
2o, K
2o, MgO, BaO, F
2total content be, below 10%, particularly to be preferably below 5%.
Except mentioned component, the composition (CaO, SrO etc.) that can also add other is to for example 10%.
Preferably do not contain in fact transition metal oxide.Thus, easily improve thermostability.At this, " not containing in fact transition metal oxide " refers to, the content of the transition metal oxide during glass forms is less than 3000ppm (quality), preferably is less than the situation (following same) of 1000ppm (quality).
Consider from the viewpoint of environment, preferably do not contain in fact PbO.At this, " not containing in fact PbO " refers to, the content of the PbO during glass forms is less than the situation of 1000ppm (quality) (following same).
As glass powder, also preferably contain Bi
2o
3glass powder.Contain Bi
2o
3glass powder as glass form in following oxide compound, convert mole mean %, preferably contain 20%～60% Bi
2o
3, 10%～35% B
2o
3, 5%～40% ZnO, 5%～30% CuO+Fe
2o
3.Below show the reason that is defined as above the glass compositing range.It should be noted that, in the explanation of following glass compositing range, as long as no specified otherwise, % means to refer to % by mole.
Bi
2o
3be the main component for reducing softening temperature, its content is 20%～60%, is preferably 25%～55%, more preferably 30%～55%.If Bi
2o
3content be less than 20%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.On the other hand, if Bi
2o
3content more than 60%, glass is to thermally labile, the easy devitrification of glass during melting or during the laser sealing-in.
B
2o
3be the composition that is used to form the glass network of bismuth glass, its content is 10%～35%, is preferably 15%～30%, more preferably 15%～28%.If B
2o
3content be less than 10%, glass is to thermally labile, the easy devitrification of glass during melting or during the laser sealing-in.On the other hand, if B
2o
3content more than 35%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
ZnO is while suppressing melting or the devitrification during laser sealing-in and the composition that thermal expansivity is reduced, and its content is 5%～40%, is preferably 5%～35%, more preferably 5%～33%.If the content of ZnO is less than 5%, be difficult to obtain above-mentioned effect.On the other hand, if the content of ZnO more than 40%, the one-tenth balance-dividing of glass in forming suffers damage, on the contrary the easy devitrification of glass.
CuO+Fe
2o
3be the composition with optical absorption characteristics, and be if irradiate the laser of the luminescence center wavelength with regulation, absorbing laser, make easily softening composition of glass.In addition, CuO+Fe
2o
3it is while suppressing melting or the composition of the devitrification during laser sealing-in.CuO+Fe
2o
3content be 5%～30%, be preferably 7%～25%, more preferably 10%～20%.CuO+Fe
2o
3if content be less than 5%, optical absorption characteristics deficiency, even irradiating laser, glass also is difficult to soften.On the other hand, if CuO+Fe
2o
3content more than 30%, the one-tenth balance-dividing of glass in forming suffers damage, on the contrary the easy devitrification of glass.
CuO is the composition with optical absorption characteristics, if or irradiate the laser of the luminescence center wavelength with regulation, absorbing laser, make easily softening composition of glass, and be while suppressing melting or the composition of the devitrification during laser sealing-in.The content of CuO is preferably 0%～25%, 5%～25%, 10%～25%, and particularly 10～20%.If the content of CuO is more than 25%, the one-tenth balance-dividing in the glass composition suffers damage, on the contrary the easy devitrification of glass.It should be noted that, as long as the content of CuO is limited in more than 5%, optical absorption characteristics improves, and during the laser sealing-in, glass is easily softening.
Fe
2o
3the composition with optical absorption characteristics, if or irradiate the laser of the luminescence center wavelength with regulation, absorbing laser, make easily softening composition of glass, and be while suppressing melting or the composition of the devitrification during laser sealing-in.Fe
2o
3content be preferably 0%～10%, 0.1%～10%, 0.2%～10%, particularly 0.5～10%.If Fe
2o
3content more than 10%, the one-tenth balance-dividing of glass in forming suffers damage, on the contrary the easy devitrification of glass.It should be noted that, as long as by Fe
2o
3content be limited in more than 0.1%, optical absorption characteristics improves, during the laser sealing-in, glass is easily softening.
Fe ion in ferric oxide is with Fe
2+or Fe
3+state exist.In the present invention, the Fe ion in ferric oxide is not restricted to Fe
2+or Fe
3+in a certain, and can be any one.Therefore, in the present invention, even at Fe
2+situation under, also can be scaled Fe
2o
3basis on processed.Particularly, in the situation that use infrared laser as irradiating light, Fe
2+there is absorption peak at region of ultra-red, therefore preferred Fe
2+ratio large, for example, preferably by the Fe in ferric oxide
2 +/ Fe
3+proportional limit be made as more than 0.03 and (be preferably more than 0.08).
Except mentioned component, for example, can add following composition.
SiO
2it is the composition that improves water tolerance.SiO
2content be preferably 0%～10%, particularly 0%～3%.If SiO
2content more than 10%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
Al
2o
3it is the composition that improves water tolerance.Al
2o
3content be preferably 0%～5%, particularly 0%～2%.If Al
2o
3content more than 5%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
MgO+CaO+SrO+BaO (the total content of MgO, CaO, SrO and BaO) is while suppressing melting or the composition of the devitrification during laser sealing-in, and the content of MgO+CaO+SrO+BaO is preferably 0%～20%, particularly 0%～15%.If the content of MgO+CaO+SrO+BaO is more than 20%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
MgO, CaO and SrO are while suppressing melting or the composition of the devitrification during laser sealing-in.The content of each composition is preferably 0%～5%, and particularly 0%～2%.If the content of each composition is more than 5%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
BaO is while suppressing melting or the composition of the devitrification during laser sealing-in.The content of BaO is preferably 0%～15%, and particularly 0%～10%.If the content of BaO is more than 15%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
CeO
2and Sb
2o
3it is while suppressing melting or the composition of the devitrification during laser sealing-in.The content of each composition is preferably 0%～5%, 0～2%, and particularly 0～1%.If the content of each composition is more than 5%, the one-tenth balance-dividing in the glass composition suffers damage, on the contrary the easy devitrification of glass.It should be noted that, consider from the viewpoint that improves thermostability, preferably Sb
2o
3for indium addition, particularly, preferably add the Sb more than 0.05%
2o
3.
WO
3it is while suppressing melting or the composition of the devitrification during laser sealing-in.WO
3content be preferably 0%～10%, particularly 0%～2%.If WO
3content more than 10%, the one-tenth balance-dividing of glass in forming suffers damage, on the contrary the easy devitrification of glass.
In
2o
3+ Ga
2o
3(In
2o
3and Ga
2o
3total content) be while suppressing melting or the composition of the devitrification during laser sealing-in.In
2o
3+ Ga
2o
3content be preferably 0%～5%, particularly 0%～3%.If In
2o
3+ Ga
2o
3content more than 5%, job order cost is surging.It should be noted that In
2o
3content more preferably 0%～1%, Ga
2o
3content more preferably 0%～0.5%.
The oxide compound of Li, Na, K and Cs is the composition that softening temperature is reduced, but promotes the effect of devitrification owing to having melting, therefore preferably to add up to content meter to be restricted to, is less than 1%.
P
2o
5it is the composition of the devitrification while suppressing melting.But, if P
2o
5content more than 1%, the easy phase-splitting of glass during melting.
La
2o
3, Y
2o
3and Gd
2o
3be the composition of the phase-splitting while suppressing melting, if still the total content of these compositions is more than 3%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
NiO, V
2o
5, CoO, MoO
3, TiO
2and MnO
2be the composition with optical absorption characteristics, and be if irradiate the laser of the luminescence center wavelength with regulation, absorbing laser, make easily softening composition of glass.The content of each composition is preferably 0%～7%, and particularly 0%～3%.If the content of each composition is more than 7%, the easy devitrification of glass during the laser sealing-in.
PbO is the composition that softening temperature is reduced, and is possible to environment, bring the composition of impact.Therefore, the content of PbO preferably is less than 0.1%.
Even the composition beyond above-mentioned, as long as in the scope of not damaging glass performance, for example can be added into 5%.
The median size D of glass powder
50for being less than 15 μ m, 0.5 μ m～10 μ m, be particularly preferably 1 μ m～5 μ m.If the median size D by glass powder
50be restricted to and be less than 15 μ m, easily make narrow and smallization of gap between two glass substrates, in this case, the needed time shorten of laser sealing-in, and even there is difference in the thermal expansivity of the thermal expansivity of seal, sealing materials layer and glass substrate, sealing-in part, glass substrate also are difficult to occur crackle etc.
The maximum particle diameter D of glass powder
99be below 15 μ m, below 10 μ m, be particularly preferably below 7 μ m.If the maximum particle diameter D by glass powder
99be restricted to below 15 μ m, easily make narrow and smallization of gap between glass substrate, in this case, the needed time shorten of laser sealing-in, and even there is difference in the thermal expansivity of the thermal expansivity of seal, sealing materials layer and glass substrate, sealing-in part, glass substrate also are difficult to occur crackle etc.
The blending ratio of the glass powder in inorganic powder and resistivity against fire filler is counted 65%～90%:10%～35% with volume %, is particularly preferably 67%～80%:20%～33%.If the content of resistivity against fire filler is more than 35 volume %, the softening mobility of seal, sealing materials is hindered, and the surface smoothness of seal, sealing materials layer easily reduces.Consequently, the efficiency of laser sealing-in easily reduces.It should be noted that, if the content of resistivity against fire filler is less than 10 volume %, be difficult to enjoy the above-mentioned effect that the resistivity against fire filler produces.
The median size D of resistivity against fire filler
50be below 2 μ m, below 1.7 μ m, be particularly preferably 0.1 μ m～1.5 μ m.If the median size D of resistivity against fire filler
50excessive, the thickness of seal, sealing materials layer is local easily becomes large, and the gap between glass substrate is inhomogeneous, and the reliability of laser sealing-in easily reduces.
The maximum particle diameter D of resistivity against fire filler
99be below 5 μ m, below 4 μ m, be particularly preferably 0.2 μ m～3 μ m.If the maximum particle diameter D of resistivity against fire filler
99excessive, the thickness of seal, sealing materials layer is easily local becomes large, and the gap between glass substrate is inhomogeneous, and the reliability of laser sealing-in easily reduces.
As the resistivity against fire filler, can use zircon, zirconium white, stannic oxide, quartz, β-triphane, trichroite, mullite, silica glass, beta-eucryptite, β-quartz, zirconium phosphate, phosphoric acid wolframic acid zirconium, wolframic acid zirconium, NbZr (PO
4)
3deng there is [AB
2(MO
4)
3] essential structure compound,
A:Li, Na, K, Mg, Ca, Sr, Ba, Zn, Cu, Ni, Mn etc.
B:Zr, Ti, Sn, Nb, Al, Sc, Y etc.
M:P, Si, W, Mo etc.
Perhaps their sosoloid.
In above-mentioned resistivity against fire filler, preferably phosphoric acid zirconium, trichroite, phosphoric acid wolframic acid zirconium.These resistivity against fire fillers have the character that thermal expansivity is low and physical strength is high, and with the glass powder that contains SnO or contain Bi
2o
3the suitability of glass powder good.
In above-mentioned seal, sealing materials, the content of inorganic powder is 97.5 quality %～100 quality %, and 99.3 quality %～99.8 quality % are particularly preferably 99.4 quality %～99.7 quality %.If the content of inorganic powder is very few, the softening illiquidity of seal, sealing materials layer during the laser sealing-in, and be difficult to improve sealing strength.It should be noted that, in the situation that the glass powder that use contains SnO, as glass powder, preferably adds pigment beyond inorganic powder, in this case, if the content of inorganic powder is too much, the content of pigment tails off relatively, therefore is difficult to laser is converted to heat energy.
In the situation that add pigment in seal, sealing materials, the content of pigment is 0.2 quality %～2.5 quality %, 0.2 quality %～0.7 quality %, is particularly preferably 0.3 quality %～0.6 quality %.If the content of pigment is very few, be difficult to laser is converted to heat energy.On the other hand, if the content of pigment is too much, during the laser sealing-in, the seal, sealing materials layer is by superheated, the thermal degradation when of generating device, and the easy devitrification of glass sealing, and sealing strength easily reduces.
The median size D of the primary particle of pigment
50for 1nm～100nm, 3nm～70nm, 5nm～60nm, be particularly preferably 10nm～50nm.If the primary particle of pigment is too small, pigment easily aggegation each other therefore is difficult to make pigment dispersed in seal, sealing materials, and during the laser sealing-in, glass powder possibly can't soften mobile partly.In addition, even the primary particle of pigment is excessive, in seal, sealing materials, also be difficult to make pigment dispersed, during the laser sealing-in, glass powder possibly can't soften mobile partly.
As pigment, preferred inorganic pigments, more preferably select white carbon, Co
3o
4, CuO, Cr
2o
3, Fe
2o
3, MnO
2, SnO, Ti
no
2n-1one or more in (n is integer), be particularly preferably carbon.These pigment are excellence aspect color developing, and the absorptivity of laser is good.It should be noted that, as glass powder, in use, contain Bi
2o
3the situation of glass powder under, from the viewpoint of suitability, consider, pigment optimization is one or more oxide based pigment that comprise in Cu, Cr, Fe, Mn.
As carbon, be preferably amorphous carbon, graphite.These carbon have easily the median size D of primary particle
50be processed as the character of 1nm～100nm.
From the viewpoint of environment, it is oxide compound that preferred pigments does not contain in fact Cr.At this, " not contain in fact Cr be oxide compound " refer to that Cr in pigment is the situation (following same) that the content of oxide compound is less than 1000ppm (quality).
The softening temperature of seal, sealing materials is below 500 ℃, below 470 ℃, below 450 ℃, below 420 ℃, is particularly preferably below 400 ℃.If softening temperature is higher than 500 ℃, the laser sealing-in easily reduces.The lower limit of softening temperature is not particularly limited, if consider the thermostability of glass powder, preferably softening temperature is limited in more than 300 ℃.
Preferably that above-mentioned seal, sealing materials and material containing is mixing, and be processed into the seal, sealing materials paste.Thus, can improve coating workability etc.It should be noted that, material containing comprises resin glue and solvent usually.
As resin glue, aliphatic poly ethylene series carbonic ether is arranged, be particularly preferably polymerized thylene carbonate ethyl ester, poly (propylene carbonate).These resin glues have when unsticking mixture or laser sealing-in, and the glass powder that make glass powder, particularly contains SnO is difficult to rotten feature.
As solvent, be preferably and select white N, one or more in N '-dimethyl formamide, ethylene glycol, dimethyl sulfoxide (DMSO), methylcarbonate, Texacar PC, butyrolactone, caprolactone, METHYLPYRROLIDONE, diglycol monotertiary phenylate (PhDG), dibutyl phthalate (DBP), ethylene glycol monobenzyl ether (BzG), diglycol monotertiary benzyl oxide (BzDEG), ethyleneglycol monophenylether (PhG).These solvents have when unsticking mixture or laser sealing-in, and the glass powder that make glass powder, particularly contains SnO is difficult to rotten feature.Particularly, in these solvents, be preferably and be selected from one or more in Texacar PC, diglycol monotertiary phenylate (PhDG), dibutyl phthalate (DBP), ethylene glycol monobenzyl ether (BzG), diglycol monotertiary benzyl oxide (BzDEG), ethyleneglycol monophenylether (PhG).The boiling point of these solvents is more than 240 ℃.Therefore, if use these solvents,, when the coating operation of silk screen printing etc., easily suppress the volatilization of solvent, result is to use steadily in the long term the seal, sealing materials paste.And the affinity of diglycol monotertiary phenylate (PhDG), dibutyl phthalate (DBP), ethylene glycol monobenzyl ether (BzG), diglycol monotertiary benzyl oxide (BzDEG), ethyleneglycol monophenylether (PhG) and pigment is high.Therefore, even add on a small quantity these solvents, also can suppress the situation that in the seal, sealing materials paste, pigment separates.
In the situation that above-mentioned seal, sealing materials paste is used the glass powder that contains SnO as glass powder, preferably by the unsticking mixture in inert atmosphere, processed, particularly preferably supply in N
2unsticking mixture in atmosphere is processed.Thus, easily prevent when unsticking mixture glass powder, the rotten situation of glass powder that particularly contains SnO.
Above-mentioned seal, sealing materials paste preferably, by the laser sealing-in under inert atmosphere, particularly preferably supplies in N
2laser sealing-in in atmosphere.Thus, easily prevent when laser sealing-in glass powder, the rotten situation of glass powder that particularly contains SnO.
The surface roughness Ra of seal, sealing materials layer for be less than 0.5 μ m, 0.3 μ m following, below 0.2 μ m, be particularly preferably 0.01 μ m～below 0.15 μ m.Thus, glass substrate adaptation each other improves, and the laser sealing-in significantly improves.
The surfaceness RMS of seal, sealing materials layer for be less than 1.0 μ m, 0.7 μ m following, below 0.5 μ m, be particularly preferably 0.05 μ m～below 0.3 μ m.Thus, glass substrate adaptation each other improves, and the laser sealing-in significantly improves.
The mean thickness of seal, sealing materials layer for being less than 10 μ m, be less than 7 μ m, 0.1 μ m～5.5 μ m, be particularly preferably 1 μ m～5 μ m.Thus, even there is difference in the thermal expansivity of the thermal expansivity of seal, sealing materials layer and glass substrate, glass substrate, sealing-in part also are difficult to occur crackle etc.Result is, can make the content of resistivity against fire filler reduce, so the softening mobility of seal, sealing materials improves, thereby can improve the surface smoothness of seal, sealing materials layer.
The thickness deviation of seal, sealing materials layer is below 2 μ m, is particularly preferably below 1 μ m.Thus, glass substrate adaptation each other improves.
Surface to the seal, sealing materials layer is ground, and can improve the surface smoothness of seal, sealing materials layer, but does not preferably grind on the surface of seal, sealing materials layer.Thus, owing to not needing grinding step, therefore easily make cheap for manufacturing costization.
Now, in OLED display, as type of drive, adopt the driven with active matrix that the active components such as TFT is disposed to each pixel and drives.In the case, OLED display is used non-alkali glass (for example, the OA-10G processed of Nippon Electric Glass Co., Ltd) with glass substrate.The thermal expansivity of non-alkali glass is generally 40 * 10
-7/ ℃ below.Usually, need to make the matched coefficients of thermal expansion of thermal expansivity and the glass substrate of seal, sealing materials, but in the situation that the thickness of seal, sealing materials layer is less than 10 μ m, particularly is less than 5 μ m, the thermal strain quantitative change caused by difference of thermal expansion coefficient is little, even therefore the thermal expansivity of seal, sealing materials is higher to a certain extent, also can carry out well hermetic seal.And, if improve the thermal expansivity of seal, sealing materials, may make the content of resistivity against fire filler reduce, so the softening mobility of seal, sealing materials improve, may improve the surface smoothness of seal, sealing materials layer.Therefore, in seal, sealing materials, thermal expansivity is preferably 60 * 10
-7/ ℃ more than and 85 * 10
-7/ ℃ below.
Preferably use the above-mentioned glass substrate with the seal, sealing materials layer, make organic EL device.
The<the 2 working of an invention mode >
The manufacture method of the electron device that the 2nd working of an invention mode is related, it has following operation: (1) prepares the operation of glass substrate; (2) material containing that will comprise the seal, sealing materials of glass powder and comprise organic binder bond mixes, and makes the operation of seal, sealing materials paste; (3) operation of the described seal, sealing materials paste formation of coating coating layer on described glass substrate; (4) described coating layer is burnt till, obtained the operation with the glass substrate of seal, sealing materials layer; (5) across described seal, sealing materials layer, the operation that the described glass substrate with the seal, sealing materials layer is overlapped with the glass substrate that does not form the seal, sealing materials layer; And (6) reach the mode irradiating laser below firing temperature with the laser sealing temperature, make the described glass substrate with the seal, sealing materials layer and do not form the operation of the glass substrate hermetic seal of described seal, sealing materials layer.
In the engineering of above-mentioned (2), as the method for mixing seal, sealing materials and material containing, aspect uniformity, the method for preferably using the kneading devices such as roller mill, ball mill, ball mill to be mixed.At this, roller mill is for take shredding unit and the application apparatus thereof of the agglutination particle that 3 rollers are representative, and ball mill is to using the media agitator mill of driven bead as medium.As ball mill, not only refer to that ball by making pottery system etc. rotates the sense stricto ball mill that carries out function that agglutination particle is pulverized in container, goes back involving vibrations ball mill, medium planetary ball mill etc.
In the operation of above-mentioned (3), as the method for coating seal, sealing materials paste, the printing of preferably being implemented by screen process press, the coating of being implemented by point gum machine.Thus, can form efficiently coating layer.
In the operation of above-mentioned (4), the preferred inert atmosphere of firing atmosphere, be particularly preferably N
2atmosphere.Thus, glass powder, particularly SnO-P
2o
5the glass frit end is difficult to go bad.
Firing temperature is preferably more than 460 ℃, more than 470 ℃, particularly more than 480 ℃.Thus, before the laser sealing-in, the gas that seal, sealing materials self comprises is released, so during the laser sealing-in, emits gas volume and tail off.
In the situation that be provided with in addition, organic binder bond is burned to the operation remove, preferably burnt till at the second-order transition temperature higher than glass powder and the temperature lower than the second-order transition temperature of seal, sealing materials.Thus, can promote the decomposition volatilization of organic binder bond.Remain on higher than the second-order transition temperature of glass powder and lower than time of the second-order transition temperature of seal, sealing materials be more than 1 minute, be particularly preferably more than 5 minutes, be below 2 hours in addition, be particularly preferably below 1 hour.If the hold-time is too short, the decomposition of organic binder bond volatilization may be insufficient.On the other hand, if the hold-time is long, with the manufacture Efficiency Decreasing of the glass substrate of seal, sealing materials layer.
In this case, preferably carry out continuously organic binder bond is burned to the operation of removing and the operation that coating layer is burnt till, more preferably carry out two-step simultaneously.Thus, the manufacture efficiency with the glass substrate of seal, sealing materials layer improves.
In the operation of above-mentioned (6), the laser sealing temperature is set to reach the mode (be preferably than below the temperature of low 10 ℃ of firing temperature, particularly than below the temperature of low 20 ℃ of firing temperature) below firing temperature.If irradiating laser under this temperature condition, only the part of corresponding sealing-in is carried out local heating, therefore can prevent the thermal degradation when of the element of electron device, and can improve the long-term reliability of electron device.
The laser sealing temperature particularly is preferably below 500 ℃, below 490 ℃, below 480 ℃, below 470 ℃, particularly below 460 ℃.Thus, during the laser sealing-in, emit gas volume and tail off.
The laser sealing-in can be used various laser.Particularly semiconductor laser, YAG laser, CO
2laser, excimer laser, infrared laser etc. are preferred aspect maneuverable.
The preferred inert atmosphere of the atmosphere of laser sealing-in, be particularly preferably N2 atmosphere.Thus, glass powder, particularly SnO-P during the laser sealing-in
2o
5the glass frit end is difficult to go bad.
Next, about the manufacture method of the electron device of present embodiment, below suitable material is formed and describes.
Seal, sealing materials preferably contains the inorganic powder 97.5 quality % that comprise glass powder～100 quality %, pigment 0 quality %～2.5 quality %, more preferably contains the inorganic powder 99 quality % that comprise glass powder～99.95 quality %, pigment 0.05 quality %～1 quality %.Particularly, the content of inorganic powder is preferably 99.5 quality %～99.9 quality %.If the content of inorganic powder is less than 97.5 quality %, during the laser sealing-in, the softening illiquidity of seal, sealing materials, be difficult to improve sealing strength in addition.The content of pigment is 0.05 quality %～1 quality %, is particularly preferably 0.1 quality %～0.5 quality %.If the content of pigment is very few, be difficult to laser is converted to heat energy.On the other hand, if the content of pigment is too much, during the laser sealing-in, seal, sealing materials is by superheated, and thermal degradation when occurs organic EL etc., and seal, sealing materials taken in excess laser, during the laser sealing-in, the temperature of seal, sealing materials layer rises undeservedly, and result is emitted gas volume may become many.And then, the easy devitrification of glass, sealing strength easily reduces.
Glass powder can utilize various glass to be, but considers from the viewpoint of thermostability, water tolerance, is suitably Bi
2o
3-B
2o
3be glass, SnO-P
2o
5be glass, V
2o
5be glass.Particularly, the viewpoint from the low melting point characteristic, be suitably SnO-P
2o
5be glass.Consider from the viewpoint of sealing strength, be suitably Bi
2o
3-B
2o
3be glass.At this, "～be glass " refer to that comprising the composition of expressing is the glass more than 20 % by mole as essential component and its total content.
SnO-P
2o
5the glass frit end as glass form in following oxide compound, convert % by mole, preferably contain, 35%～70% SnO, 10～30% P
2o
5.Below show the reason that is defined as above the glass compositing range.It should be noted that, in the explanation of glass compositing range, except the situation of specified otherwise, % means to refer to % by mole.
SnO is the composition that the glass eutectic is revealed.The content of SnO is 35%～70%, 40%～70%, is particularly preferably 50%～68%.It should be noted that, as long as the content of SnO is more than 50%, easy softening the flowing of glass during the laser sealing-in.If the content of SnO is less than 35%, the viscosity of glass becomes too high, is difficult to use desirable Laser output to carry out the laser sealing-in.On the other hand, if the content of SnO, more than 70%, is difficult to vitrifying.
P
2o
5be network former, and be the composition that improves thermostability.P
2o
5content be 10～30%, 15%～27%, be particularly preferably 15%～25%.If P
2o
5content be less than 10%, thermostability easily reduces.On the other hand, if P
2o
5content more than 30%, weathering resistance reduces, and is difficult to guarantee the long-term reliability of organic EL device etc.
Except mentioned component, can also add following composition.
ZnO is intermidate oxide, and is the composition that makes stabilization.The content of ZnO is 0%～30%, 1%～20%, is particularly preferably 1%～15%.If the content of ZnO is more than 30%, thermostability easily reduces.
B
2o
3be network former, still make the composition of stabilization, and be the composition that improves weathering resistance.B
2o
3content be 0%～25%, 1%～20%, be particularly preferably 2%～15%.If B
2o
3content more than 20%, the viscosity of glass becomes too high, is difficult to use desirable laser output power to carry out the laser sealing-in.
Al
2o
3be intermidate oxide, still make the composition of stabilization, and be the composition that thermal expansivity is reduced.Al
2o
3content be 0%～10%, 0.1%～10%, be particularly preferably 0.5～5%.If Al
2o
3content more than 10%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
SiO
2be network former, still make the composition of stabilization.SiO
2content be 0%～15%, be particularly preferably 0%～5%.If SiO
2content more than 15%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
In
2o
3it is the composition that improves thermostability.In
2o
3content be preferably 0%～5%.If In
2o
3content more than 5%, job order cost is surging.
Ta
2o
5it is the composition that improves thermostability.Ta
2o
5content be preferably 0%～5%.If Ta
2o
5content more than 5%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
La
2o
3being the composition that improves thermostability, is the composition that improves weathering resistance in addition.La
2o
3content be preferably 0%～15%, 0%～10%, be particularly preferably 0%～5%.If La
2o
3content more than 15%, job order cost is surging.
MoO
3it is the composition that improves thermostability.MoO
3content be preferably 0%～5%.If MoO
3content more than 5%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
WO
3it is the composition that improves thermostability.WO
3content be preferably 0%～5%.If WO
3content more than 5%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
Li
2o is the composition that the glass eutectic is revealed.Li
2the content of O is preferably 0%～5%.If Li
2the content of O is more than 5%, and thermostability easily reduces.Na
2o is the composition that the glass eutectic is revealed.Na
2the content of O is preferably 0%～10%, is particularly preferably 0%～5%.If Na
2the content of O is more than 10%, and thermostability easily reduces.K
2o is the composition that the glass eutectic is revealed.K
2the content of O is preferably 0%～5%.If K
2the content of O is more than 5%, and thermostability easily reduces.
MgO is the composition that improves thermostability.The content of MgO is preferably 0%～15%.If the content of MgO is more than 15%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
BaO is the composition that improves thermostability.The content of BaO is preferably 0%～10%.If the content of BaO is more than 10%, the one-tenth balance-dividing that glass forms suffers damage, on the contrary the easy devitrification of glass.
F
2it is the composition that the glass eutectic is revealed.The content of F2 is preferably 0%～5%.If F
2content more than 5%, thermostability easily reduces.
If consider thermostability and low melting point characteristic, In
2o
3, Ta
2o
5, La
2o
3, MoO
3, WO
3, Li
2o, Na
2o, K
2o, MgO, BaO, and F
2total content be preferably below 10%.
Except mentioned component, can also add for example to 10% of other compositions (CaO, SrO etc.).
Above-mentioned SnO-P
2o
5the glass frit end, preferably do not comprise in fact transition metal oxide.Thus, can prevent glass taken in excess laser, thereby the temperature of seal, sealing materials layer is than reasonably rising during the laser sealing-in, result is emitted the many situations of gas quantitative change, and the thermostability of glass is difficult to reduce.
As glass powder, preferred Bi also
2o
3-B
2o
3the glass frit end.Bi
2o
3-B
2o
3the glass frit end forms mole expression % converted in following oxide compound as glass, preferably contain 20%～60% Bi
2o
3, 10%～35% B
2o
3, 5%～40% ZnO, 5%～30% CuO+Fe
2o
3.Below show the reason that is defined as above the glass compositing range.It should be noted that, in the explanation of following glass compositing range, except the situation of specified otherwise, % means to refer to % by mole.
Bi
2o
3be the main component for reducing softening temperature, its content is 20%～60%, is preferably 25%～55%, more preferably 30%～55%.If Bi
2o
3content be less than 20%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.On the other hand, if Bi
2o
3content more than 60%, glass is to thermally labile, the easy devitrification of glass during melting or during the laser sealing-in.
B
2o
3be the composition that forms the glass network of bismuth glass, its content is 10%～35%, is preferably 15%～30%, more preferably 15%～28%.If B
2o
3content be less than 10%, glass is to thermally labile, the easy devitrification of glass during melting or during the laser sealing-in.On the other hand, if B
2o
3content more than 35%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
ZnO is while suppressing melting or the devitrification during laser sealing-in and the composition that thermal expansivity is reduced, and its content is 5%～40%, is preferably 5%～35%, more preferably 5%～33%.If the content of ZnO is less than 5%, be difficult to obtain above-mentioned effect.On the other hand, if the content of ZnO more than 40%, the one-tenth balance-dividing of glass in forming suffers damage, on the contrary the easy devitrification of glass.
CuO+Fe
2o
3be the composition with optical absorption characteristics, and be if irradiate the laser of the luminescence center wavelength with regulation, absorbing laser, make easily softening composition of glass.In addition, CuO+Fe
2o
3it is while suppressing melting or the composition of the devitrification during laser sealing-in.CuO+Fe
2o
3content be 5%～30%, be preferably 7%～25%, more preferably 10%～20%.If CuO+Fe
2o
3content be less than 5%, optical absorption characteristics deficiency, even irradiating laser, glass also is difficult to soften.On the other hand, if CuO+Fe
2o
3content more than 30%, the one-tenth balance-dividing of glass in forming suffers damage, on the contrary the easy devitrification of glass.
CuO is the composition with optical absorption characteristics, if or irradiate the laser of the luminescence center wavelength with regulation, absorbing laser, make easily softening composition of glass, and be while suppressing melting or the composition of the devitrification during laser sealing-in.The content of CuO is preferably 0%～25%, 5%～25%, 10%～25%, and particularly 10%～20%.If the content of CuO is more than 25%, the one-tenth balance-dividing in the glass composition suffers damage, on the contrary the easy devitrification of glass.It should be noted that, as long as the content of CuO is restricted to more than 5%, optical absorption characteristics improves, and during the laser sealing-in, glass is easily softening.
Fe
2o
3the composition with optical absorption characteristics, if or irradiate the laser of the luminescence center wavelength with regulation, absorbing laser, make easily softening composition of glass, and be while suppressing melting or the composition of the devitrification during laser sealing-in.Fe
2o
3content be preferably 0%～10%, 0.1%～10%, 0.2%～10%, particularly 0.5%～10%.If Fe
2o
3content more than 10%, the one-tenth balance-dividing of glass in forming suffers damage, on the contrary the easy devitrification of glass.It should be noted that, as long as by Fe
2o
3content be restricted to more than 0.1%, optical absorption characteristics improves, during the laser sealing-in, glass is easily softening.
Fe ion in ferric oxide is with Fe
2+or Fe
3+state exist.Fe ion in ferric oxide is not restricted to Fe
2+or Fe
3+in a certain, and can be any one.Therefore, even at Fe
2+situation under, also can be scaled Fe
2o
3basis on processed.Particularly, in the situation that use infrared laser as irradiating light, Fe
2+there is absorption peak at region of ultra-red, therefore preferred Fe
20ratio large, for example, preferably by the Fe in ferric oxide
2+/ Fe
3+proportional limit be made as more than 0.03 and (be preferably more than 0.08).
Except mentioned component, for example, can also add following composition.
SiO
2it is the composition that improves water tolerance.SiO
2content be preferably 0%～10%, particularly 0%～3%.If SiO
2content more than 10%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
Al
2o
3it is the composition that improves water tolerance.Al
2o
3content be preferably 0%～5%, particularly 0%～2%.If Al
2o
3content more than 5%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
MgO+CaO+SrO+BaO (the total content of MgO, CaO, SrO and BaO) is while suppressing melting or the composition of the devitrification during laser sealing-in, and the content of MgO+CaO+SrO+BaO is preferably 0%～20%, particularly 0%～15%.If the content of MgO+CaO+SrO+BaO is more than 20%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
MgO, CaO and SrO are while suppressing melting or the composition of the devitrification during laser sealing-in.The content of each composition is preferably 0%～5%, and particularly 0%～2%.If the content of each composition is more than 5%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
BaO is while suppressing melting or the composition of the devitrification during laser sealing-in.The content of BaO is preferably 0%～15%, and particularly 0%～10%.If the content of BaO is more than 15%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
CeO
2and Sb
2o
3it is while suppressing melting or the composition of the devitrification during laser sealing-in.The content of each composition is preferably 0%～5%, 0%～2%, and particularly 0%～1%.If the content of each composition is more than 5%, the one-tenth balance-dividing in the glass composition suffers damage, on the contrary the easy devitrification of glass.It should be noted that, consider Sb from the viewpoint that improves thermostability
2o
3be preferably indium addition, particularly preferably add the Sb more than 0.05%
2o
3.
WO
3it is while suppressing melting or the composition of the devitrification during laser sealing-in.WO
3content be preferably 0%～10%, particularly 0%～2%.If WO
3content more than 10%, the one-tenth balance-dividing of glass in forming suffers damage, on the contrary the easy devitrification of glass.
In
2o
3+ Ga
2o
3(In
2o
3and Ga
2o
3total content) be while suppressing melting or the composition of the devitrification during laser sealing-in.In
2o
3+ Ga
2o
3content be preferably 0%～5%, particularly 0%～3%.If In
2o
3+ Ga
2o
3content more than 5%, job order cost is surging.It should be noted that, more preferably In
2o
3content be 0%～1%, more preferably Ga
2o
3content be 0%～0.5%.
The oxide compound of Li, Na, K and Cs is the composition that softening temperature is reduced, and promotes the effect of devitrification while having melting, therefore preferably to add up to content meter, is restricted to and is less than 1%.
P
2o
5it is the composition of the devitrification while suppressing melting.But, if P
2o
5content more than 1%, the easy phase-splitting of glass during melting.
La
2o
3, Y
2o
3and Gd
2o
3the composition of the phase-splitting while suppressing melting, if the total content of these compositions more than 3%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
NiO, V
2o
5, CoO, MoO
3, TiO
2and MnO
2be the composition with optical absorption characteristics, and be if irradiate the laser of the luminescence center wavelength with regulation, absorbing laser, make easily softening composition of glass.The content of each composition is preferably 0%～7%, and particularly 0%～3%.If the content of each composition is more than 7%, the easy devitrification of glass during the laser sealing-in.
PbO is the composition that softening temperature is reduced, and is possible to environment, bring the composition of impact.Therefore, the content of PbO is preferably and is less than 0.1%.
Even the composition beyond above-mentioned, as long as in the scope of not damaging glass performance, for example can be added into 5%.
From the viewpoint of environment, consider, the preferred glass powder does not contain in fact PbO.
The median size D of glass powder
50for being less than 15 μ m, 0.5 μ m～10 μ m, be particularly preferably 1 μ m～5 μ m.If the median size D by glass powder
50be restricted to and be less than 15 μ m, easily make narrow and smallization of gap between glass substrate, in this case, the needed time shorten of laser sealing-in, and there is difference in the thermal expansivity of glass substrate and seal, sealing materials, the interface of glass substrate and seal, sealing materials layer also is difficult to occur crackle etc.
The maximum particle diameter D of glass powder
99be below 30 μ m, below 20 μ m, be particularly preferably below 10 μ m.If the maximum particle diameter D by glass powder
99be restricted to below 30 μ m, easily make narrow and smallization of gap between glass substrate, in this case, the needed time shorten of laser sealing-in, even, and there is difference in the thermal expansivity of glass substrate and seal, sealing materials, the interface of glass substrate and seal, sealing materials layer also is difficult to occur crackle etc.
Inorganic powder also preferably comprises the resistivity against fire filler.Thus, can be that the thermal expansivity of seal, sealing materials reduces, and can improve the physical strength of seal, sealing materials.The blending ratio of the glass powder in inorganic powder and resistivity against fire filler is counted 40%～100%:0%～60%, 40%～99.9%:0.1%～60%, 45%～90%:10%～55%, 50%～80%:20%～50%, 50%～70%:30%～50% with volume %, is particularly preferably 50%～65%:35%～50%.If the content of resistivity against fire filler is more than 60 volume %, the ratio of glass powder tails off relatively, and the efficiency of laser sealing-in easily reduces.It should be noted that, if the content of resistivity against fire filler is less than 0.1 volume %, be difficult to enjoy the effect produced by the resistivity against fire filler.
As the resistivity against fire filler, can use zircon, zirconium white, stannic oxide, quartz, β-triphane, trichroite, mullite, silica glass, beta-eucryptite, β-quartz, zirconium phosphate, phosphoric acid wolframic acid zirconium, wolframic acid zirconium, NbZr (PO
4)
3deng there is [AB
2(MO
4)
3] essential structure compound,
A:Li, Na, K, Mg, Ca, Sr, Ba, Zn, Cu, Ni, Mn etc.
B:Zr, Ti, Sn, Nb, Al, Sc, Y etc.
M:P, Si, W, Mo etc.
Perhaps their sosoloid.
The maximum particle diameter D99 of resistivity against fire filler is below 20 μ m, below 15 μ m, is particularly preferably below 10 μ m.If the maximum particle diameter D of resistivity against fire filler
99be greater than 20 μ m,, in the sealing-in part, easily produce the position with the above thickness of 30 μ m, therefore, in OLED display, the gap between glass substrate becomes inhomogeneous, is difficult to make the OLED display slimming.In addition, if by the maximum particle diameter D of resistivity against fire filler
99be restricted to below 20 μ m, easily make narrow and smallization of gap between glass substrate, in this case, the needed time shorten of laser sealing-in, even, and there is difference in the thermal expansivity of glass substrate and seal, sealing materials, the interface of glass substrate and seal, sealing materials layer also is difficult to crack etc.
The pigment optimization added in seal, sealing materials is mineral dye, more preferably selects white carbon, Co
3o
4, CuO, Cr
2o
3, Fe
2o
3, MnO
2, SnO, TinO
2n-1one or more in (n is integer), spinel system complex oxide, be particularly preferably carbon.These pigment are excellence aspect color developing, and the absorptivity of laser is good.In addition, as glass powder, using Bi
2o
3-B
2o
3be in the situation of glass, consider from the viewpoint of suitability, pigment optimization is one or more oxide based pigment that comprise in Cu, Cr, Fe, Mn.
As carbon, can use various materials, but be particularly preferably amorphous carbon, graphite.These carbon have easily the median size D of primary particle
50be machined to the character of 1nm～100nm.It should be noted that, in the situation that the glass of glass powder comprises SnO in forming, as pigment, as long as add carbon, just can expect to suppress the effect of the oxidation of SnO when burning till.
From the environment viewpoint, consider, it is oxide compound that preferred pigments does not contain in fact Cr.
Median size (the D of the primary particle of pigment
50) be 1nm～100nm, 3nm～70nm, 5nm～60nm, be particularly preferably 10～50nm.If the primary particle of pigment is too small, pigment easily aggegation each other therefore is difficult to make pigment dispersed in seal, sealing materials, and during the laser sealing-in, glass powder possibly can't soften mobile partly.In addition, even the primary particle of pigment is excessive, in seal, sealing materials, also be difficult to make pigment dispersed, during the laser sealing-in, glass powder possibly can't soften mobile partly.
The softening temperature of seal, sealing materials is below 500 ℃, below 460 ℃, below 450 ℃, below 420 ℃, is particularly preferably below 400 ℃.If softening temperature is higher than 500 ℃, the efficiency of laser sealing-in easily reduces.The lower limit of softening temperature is not particularly limited, if consider thermostability, preferably softening temperature is restricted to more than 300 ℃.
Now, in OLED display, as type of drive, adopt the driven with active matrix that the active components such as TFT is disposed to each pixel and drives.In this case, glass substrate uses non-alkali glass (for example, the OA-10G processed of Nippon Electric Glass Co., Ltd).The thermal expansivity of non-alkali glass is generally 40 * 10
-7/ ℃ below.On the other hand, the thermal expansivity of seal, sealing materials mostly is 76 * 10
- 7/ ℃～90 * 10
-7/ ℃.Therefore, in order to prevent the stress rupture of sealing-in part, need to make the thermal expansivity of seal, sealing materials tightly conform to the thermal expansivity of non-alkali glass.Therefore, if add resistivity against fire filler, the particularly NbZr (PO of low bulk in seal, sealing materials
4)
3, zirconium phosphate, trichroite, can make the thermal expansivity of seal, sealing materials significantly reduce.Therefore, in seal, sealing materials, thermal expansivity is 85 * 10
-7/ ℃ below, 75 * 10
-7/ ℃ below, 65 * 10
-7/ ℃ below, 55 * 10
-7/ ℃ below, be particularly preferably 49 * 10
-7/ ℃ below.Thus, can prevent that residual stress from diminishing, also easily preventing the stress rupture of sealing-in part.
Except glass powder, resistivity against fire filler, pigment, also can in seal, sealing materials, add granulated glass sphere etc. as spacer.
The seal, sealing materials paste comprises seal, sealing materials, material containing etc.In addition, material containing comprises resin glue, solvent usually.As required, also can in material containing, add tensio-active agent, tackifier etc.
As organic binder bond, aliphatic poly ethylene series carbonic ether is arranged, be particularly preferably polymerized thylene carbonate ethyl ester, poly (propylene carbonate).These organic binder bonds have be difficult to make glass powder, particularly SnO-P when organic binder bond are removed in burning
2o
5the character that the glass frit end is rotten.
As solvent, preferably comprise and select white N, one or more in N '-dimethyl formamide, ethylene glycol, dimethyl sulfoxide (DMSO), methylcarbonate, Texacar PC, butyrolactone, caprolactone, METHYLPYRROLIDONE, diglycol monotertiary phenylate (PhDG), dibutyl phthalate (DBP), ethylene glycol monobenzyl ether (BzG), diglycol monotertiary benzyl oxide (BzDEG), ethyleneglycol monophenylether (PhG).These solvents have and are difficult to the character that makes glass powder rotten.Particularly, in these solvents, be preferably and select one or more in white Texacar PC, diglycol monotertiary phenylate (PhDG), dibutyl phthalate (DBP), ethylene glycol monobenzyl ether (BzG), diglycol monotertiary benzyl oxide (BzDEG), ethyleneglycol monophenylether (PhG).The boiling point of these solvents is more than 240 ℃.Therefore, if use these solvents,, when the coating seal, sealing materials pastes such as use screen process press, easily suppress the volatilization of solvent, result is to use steadily in the long term the seal, sealing materials paste.And the affinity of diglycol monotertiary phenylate (PhDG), dibutyl phthalate (DBP), ethylene glycol monobenzyl ether (BzG), diglycol monotertiary benzyl oxide (BzDEG), ethyleneglycol monophenylether (PhG) and pigment is high.Therefore, even the addition of these solvents is a small amount of, also can suppress the situation that in the seal, sealing materials paste, pigment separates.
The embodiment of the<the 1 related invention >
The manufacture method of the glass substrate with the seal, sealing materials layer that the embodiment of the 1st related invention is related, it has following operation: (1) prepares the operation of glass substrate; (2) be coated with the first seal, sealing materials paste on glass substrate, then form the operation of the first seal, sealing materials film; (3) be coated with the second seal, sealing materials paste on the first seal, sealing materials film, then form the operation of the second seal, sealing materials film; (4) stacked film of gained burnt till, formed the operation of seal, sealing materials layer on described glass substrate.
The first seal, sealing materials paste comprises the first glass powder, and comprises as required material containing, resistivity against fire filler, pigment.In addition, the second seal, sealing materials paste comprises the second glass powder, comprises as required material containing, resistivity against fire filler, pigment.It is described that these compositions suitable is constructed as follows.It should be noted that, material containing comprises resin glue and solvent usually.
The median size D of the second glass powder
50be less than the median size D of the first glass powder
50.If the median size D of the second glass powder
50median size D with the first glass powder
50be in a ratio of and be equal to or larger, the surface smoothness of seal, sealing materials layer suffers damage, and is difficult to make seal, sealing materials layer and closely sealed equably by the sealing-in thing, and the laser sealing-in easily reduces.
The maximum particle diameter D of the second glass powder
99be less than the maximum particle diameter D of the first glass powder
99.If the maximum particle diameter D of the second glass powder
99maximum particle diameter D with the first glass powder
99be in a ratio of and be equal to or larger, the surface smoothness of seal, sealing materials layer suffers damage, and is difficult to make seal, sealing materials layer and closely sealed equably by the sealing-in thing, and the laser sealing-in easily reduces.
The median size D of the second glass powder
50be 0.1 μ m～2.0 μ m, be particularly preferably 0.3 μ m～1.7 μ m.If the median size D of the second glass powder
50too small, the easy devitrification of glass while burning till, softening the flowing of seal, sealing materials may be hindered, and when pulverizing, classification, the easy aggegation of glass powder, and remaining with the agglutinator form after the second seal, sealing materials paste mixing, may when silk screen printing, become screen plugging reason.On the other hand, if the median size D of the second glass powder
50excessive, the concavo-convex of the second seal, sealing materials film becomes excessive during silk screen printing, the surface smoothness of seal, sealing materials layer easily reduces, and while burning till, seal, sealing materials is difficult to softening flowing, therefore need to make firing temperature increase, in this case, easily become large by the thermal damage of sealing-in thing, and can become the reason that cost raises.It should be noted that, in order to realize the coating thickness of every 1 silk screen printing, the median size D of the second glass powder
50preferably large as far as possible, if but the thickness of the second seal, sealing materials film (wet film) is greater than 3.0 μ m, the second seal, sealing materials film is whole can produce than macrorelief, thus the seal, sealing materials layer with by the adaptation of sealing-in thing, easily reduced.
The median size D of the first glass powder
50be 1.0 μ m～3.5 μ m, be particularly preferably 1.0 μ m～2.5 μ m.If the median size D of the first glass powder
50too small, the granularity of the second glass powder must be less, the easy devitrification of glass while burning till, softening the flowing of seal, sealing materials may be hindered, and when pulverizing, classification, the easy aggegation of glass powder, and remaining with the agglutinator form after the first seal, sealing materials paste mixing, may become reason screen plugging when silk screen printing.On the other hand, if the median size D of the first glass powder
50excessive, while burning till, seal, sealing materials is difficult to softening flowing, and therefore need to make firing temperature increase, and in this case, by the thermal damage of sealing-in thing, is easily become large, may become the reason that cost raises.
The maximum particle diameter D of the second glass powder
99be 0.5 μ m～6.1 μ m, be particularly preferably 1.0 μ m～3.5 μ m.If the maximum particle diameter D of the second glass powder
99too small, the easy devitrification of glass while burning till, softening the flowing of seal, sealing materials may be hindered, and when pulverizing, classification, the easy aggegation of glass powder, remaining with the agglutinator form after the second seal, sealing materials paste mixing, may become reason screen plugging when silk screen printing.If the maximum particle diameter D of the second glass powder
99excessive, the concavo-convex excessive change of the second seal, sealing materials film is large during silk screen printing, the surface smoothness of seal, sealing materials layer easily reduces, and while burning till, seal, sealing materials is difficult to softening flowing, therefore must be that firing temperature rises, in this case, by the thermal damage of sealing-in thing, easily become large, can become the reason that cost raises.
The maximum particle diameter D99 of the first glass powder is 3.0 μ m～15.0 μ m, is particularly preferably 4.0 μ m～10.0 μ m.If the maximum particle diameter D99 of the first glass powder is too small, the granularity of the second glass powder must be less, the easy devitrification of glass while burning till, softening the flowing of seal, sealing materials may be hindered, and when pulverizing, classification, the easy aggegation of glass powder, remaining with the agglutinator form after the first seal, sealing materials paste mixing, may when silk screen printing, become screen plugging reason.On the other hand, if the maximum particle diameter D of the first glass powder
99excessive, while burning till, seal, sealing materials is difficult to softening flowing, and need to make firing temperature increase, and in this case, by the thermal damage of sealing-in thing, is become large, can become the reason that cost raises.
Glass powder (the first glass powder and the second glass powder) is preferably the glass powder that contains SnO, the glass powder that contains SnO forms mole expression % converted in following oxide compound as glass, preferably contain 35%～70% SnO, 10%～30% P
2o
5.Below show the reason that is defined as above the glass compositing range.It should be noted that, in the explanation of glass compositing range, except the situation of specified otherwise, % means to refer to % by mole.
SnO is the composition that the glass eutectic is revealed.Its content is preferably 35%～70%, 40%～70%, is particularly preferably 50%～68%.It should be noted that, if the content of SnO is more than 50%, during the laser sealing-in, glass is softening flowing easily.If the content of SnO is less than 35%, the viscosity of glass becomes too high, is difficult to use desirable laser output power to carry out the laser sealing-in.On the other hand, if the content of SnO, more than 70%, is difficult to vitrifying.
P
2o
5be network former, and be the composition that improves thermostability.Its content is preferably 10%～30%, 15%～27%, is particularly preferably 15%～25%.If P
2o
5content be less than 10%, thermostability easily reduces.On the other hand, if P
2o
5content more than 30%, weathering resistance reduces, and is difficult to guarantee the long-term reliability of organic EL device etc.
Except mentioned component, can also add following composition.
ZnO is intermidate oxide, and is the composition that makes stabilization.Its content is 0%～30%, 1%～20%, is particularly preferably 1%～15%.If the content of ZnO is more than 30%, thermostability easily reduces.
B
2o
3be network former, and make the composition of stabilization.In addition, B
2o
3it is the composition that improves weathering resistance.Its content is 0%～20%, 1%～20%, is particularly preferably 2%～15%.If B
2o
3content more than 20%, the viscosity of glass becomes too high, is difficult to use desirable laser output power to carry out the laser sealing-in.
Al
2o
3be intermidate oxide, and be the composition that makes stabilization.In addition, Al
2o
3it is the composition that thermal expansivity is reduced.Its content is 0%～10%, 0.1%～10%, is particularly preferably 0.5%～5%.If Al
2o
3content more than 10%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
SiO
2be network former, and be the composition that makes stabilization.Its content is 0%～15%, is particularly preferably 0%～5%.If SiO
2content more than 15%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
In
2o
3be the composition that improves thermostability, its content is preferably 0%～5%.If In
2o
3content more than 5%, job order cost is surging.
Ta
2o
5be the composition that improves thermostability, its content is preferably 0%～5%.If Ta
2o
5content more than 5%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
La
2o
3being the composition that improves thermostability, is the composition that improves weathering resistance in addition.Its content is 0%～15%, 0%～10%, is particularly preferably 0%～5%.If La
2o
3content more than 15%, job order cost is surging.
MoO
3be the composition that improves thermostability, its content is preferably 0%～5%.If MoO
3content more than 5%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
WO
3be the composition that improves thermostability, its content is preferably 0%～5%.If WO
3content more than 5%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
Li
2o is the composition that the glass eutectic is revealed, and its content is preferably 0%～5%.If Li
2the content of O is more than 5%, and thermostability easily reduces.
Na
2o is the composition that the glass eutectic is revealed, and its content is 0%～10%, is particularly preferably 0%～5%.If Na
2the content of O is more than 10%, and thermostability easily reduces.
K
2o is the composition that the glass eutectic is revealed, and its content is preferably 0%～5%.If K
2the content of O is more than 5%, and thermostability easily reduces.
MgO is the composition that improves thermostability, and its content is preferably 0%～15%.If the content of MgO is more than 15%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
BaO is the composition that improves thermostability, and its content is preferably 0%～10%.If the content of BaO is more than 10%, the one-tenth balance-dividing that glass forms suffers damage, on the contrary the easy devitrification of glass.
F
2be the composition that the glass eutectic is revealed, its content is preferably 0%～5%.If F
2content more than 5%, thermostability easily reduces.
If consider thermostability and low melting point characteristic, In
2o
3, Ta
2o
5, La
2o
3, MoO
3, WO
3, Li
2o, Na
2o, K
2o, MgO, BaO, F
2total content be, below 10%, to be particularly preferably below 5%.
Except mentioned component, can also add other for example to 10% of composition (CaO, SrO etc.).
With regard to the glass powder that contains SnO, preferred glass does not comprise in fact transition metal oxide in forming.Thus, can improve thermostability.
Glass powder (the first glass powder and the second glass powder) also is preferably and contains Bi
2o
3glass powder.Bi
2o
3contain glass powder and form mole expression % converted in following oxide compound as glass, preferably contain 20%～60% Bi
2o
3, 10%～35% B
2o
3, 5%～40% ZnO, 5%～30% CuO+Fe
2o
3.Below show the reason that is defined as above the glass compositing range.It should be noted that, in the explanation of following glass compositing range, except the situation of specified otherwise, % means to refer to % by mole.
Bi
2o
3be the main component for reducing softening temperature, its content is 20%～60%, is preferably 25%～55%, more preferably 30%～55%.If Bi
2o
3content be less than 20%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.On the other hand, if Bi
2o
3content more than 60%, glass is to thermally labile, the easy devitrification of glass during melting or during the laser sealing-in.
B
2o
3be the composition that forms the glass network of bismuth glass, its content is 10%～35%, is preferably 15%～30%, more preferably 15%～28%.If B
2o
3content be less than 10%, glass is to thermally labile, the easy devitrification of glass during melting or during the laser sealing-in.On the other hand, if B
2o
3content more than 35%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
ZnO is while suppressing melting or the devitrification during laser sealing-in, and the composition that thermal expansivity is reduced, and its content is 5%～40%, is preferably 5%～35%, more preferably 5%～33%.If the content of ZnO is less than 5%, be difficult to obtain above-mentioned effect.On the other hand, if the content of ZnO more than 40%, the one-tenth balance-dividing of glass in forming suffers damage, on the contrary the easy devitrification of glass.
CuO+Fe
2o
3be the composition with optical absorption characteristics, and be if irradiate the laser of the luminescence center wavelength with regulation, absorbing laser, make easily softening composition of glass.In addition, CuO+Fe
2o
3it is while suppressing melting or the composition of the devitrification during laser sealing-in.CuO+Fe
2o
3content be 5%～30%, be preferably 7%～25%, more preferably 10%～20%.If CuO+Fe
2o
3content be less than 5%, optical absorption characteristics deficiency, even irradiating laser, glass also is difficult to soften.On the other hand, if CuO+Fe
2o
3content more than 30%, the one-tenth balance-dividing of glass in forming suffers damage, on the contrary the easy devitrification of glass.
CuO is the composition with optical absorption characteristics, if or irradiate the laser of the luminescence center wavelength with regulation, absorbing laser, make easily softening composition of glass, and be while suppressing melting or the composition of the devitrification during laser sealing-in.The content of CuO is preferably 0%～25%, 5%～25%, 10%～25%, and particularly 10%～20%.If the content of CuO is more than 25%, the one-tenth balance-dividing in the glass composition suffers damage, on the contrary the easy devitrification of glass.It should be noted that, as long as the content of CuO is limited in more than 5%, optical absorption characteristics improves, and during the laser sealing-in, glass is easily softening.
Fe
2o
3the composition with optical absorption characteristics, if or irradiate the laser of the luminescence center wavelength with regulation, absorbing laser, make easily softening composition of glass, and be while suppressing melting or the composition of the devitrification during laser sealing-in.Fe
2o
3content be preferably 0%～10%, 0.1%～10%, 0.2%～10%, particularly 0.5%～10%.If Fe
2o
3content more than 10%, the one-tenth balance-dividing of glass in forming suffers damage, on the contrary the easy devitrification of glass.It should be noted that, as long as by Fe
2o
3content be limited in more than 0.1%, optical absorption characteristics improves, during the laser sealing-in, glass is easily softening.
The Fe ion comprised in glass is with Fe
2+or Fe
3+state exist.Fe ion in glass is not defined as Fe
2+or Fe
3+in a certain, and can be any one.Therefore, even at Fe
2+situation under, also can be scaled Fe
2o
3basis on processed.Particularly, in the situation that use infrared laser as irradiating light, Fe
2+there is absorption peak at region of ultra-red, therefore preferred Fe
2+ratio large, for example, preferably by the Fe in glass
2+/ Fe
3+proportional limit built in (being preferably more than 0.08) more than 0.03.
Except mentioned component, for example, can also add following composition.
SiO
2it is the composition that improves water tolerance.SiO
2content be preferably 0%～10%, particularly 0%～3%.If SiO
2content more than 10%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
Al
2o
3it is the composition that improves water tolerance.Al
2o
3content be preferably 0%～5%, particularly 0%～2%.If Al
2o
3content more than 5%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
MgO+CaO+SrO+BaO (the total content of MgO, CaO, SrO and BaO) is while suppressing melting or the composition of the devitrification during laser sealing-in, and the content of MgO+CaO+SrO+BaO is preferably 0%～20%, particularly 0%～15%.If the content of MgO+CaO+SrO+BaO is more than 20%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
MgO, CaO and SrO are while suppressing melting or the composition of the devitrification during laser sealing-in.The content of each composition is preferably 0%～5%, and particularly 0%～2%.If the content of each composition is more than 5%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
BaO is while suppressing melting or the composition of the devitrification during laser sealing-in.The content of BaO is preferably 0%～15%, and particularly 0%～10%.If the content of BaO is more than 15%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
CeO
2and Sb
2o
3it is while suppressing melting or the composition of the devitrification during laser sealing-in.The content of each composition is preferably 0%～5%, 0%～2%, and particularly 0%～1%.If the content of each composition is more than 5%, the one-tenth balance-dividing in the glass composition suffers damage, on the contrary the easy devitrification of glass.It should be noted that, consider from the viewpoint that improves thermostability, preferably Sb
2o
3for indium addition, particularly, preferably add the Sb more than 0.05%
2o
3.
WO
3it is while suppressing melting or the composition of the devitrification during laser sealing-in.WO
3content be preferably 0%～10%, particularly 0%～2%.If WO
3content more than 10%, the one-tenth balance-dividing of glass in forming suffers damage, on the contrary the easy devitrification of glass.
In
2o
3+ Ga
2o
3(In
2o
3and Ga
2o
3total content) be while suppressing melting or the composition of the devitrification during laser sealing-in.In
2o
3+ Ga
2o
3content be preferably 0%～5%, particularly 0%～3%.If In
2o
3+ Ga
2o
3content more than 5%, job order cost is surging.It should be noted that In
2o
3content more preferably 0%～1%, Ga
2o
3content more preferably 0%～0.5%.
The oxide compound of Li, Na, K and Cs is the composition that softening temperature is reduced, but promotes the effect of devitrification owing to having melting, therefore preferably to add up to content meter, is restricted to and is less than 1%.
P
2o
5it is the composition of the devitrification while suppressing melting.But, if P
2o
5content more than 1%, the easy phase-splitting of glass during melting.
La
2o
3, Y
2o
3and Gd
2o
3the composition of the phase-splitting while suppressing melting, if the total content of these compositions more than 3%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
NiO, V
2o
5, CoO, MoO
3, TiO
2and MnO
2be the composition with optical absorption characteristics, and be if irradiate the laser of the luminescence center wavelength with regulation, absorbing laser, make easily softening composition of glass.The content of each composition is preferably 0%～7%, and particularly 0%～3%.If the content of each composition is more than 7%, the easy devitrification of glass during the laser sealing-in.
PbO is the composition that softening temperature is reduced, and is possible to environment, bring the composition of impact.Therefore, the content of PbO is preferably and is less than 0.1%.
For example, even the composition beyond above-mentioned, also can, in the scope of not damaging glass performance, can be added into 5%.
From the environment viewpoint, consider, glass powder (the first glass powder and the second glass powder) does not preferably contain in fact PbO in glass forms.
Preferably the glass of the first glass powder forms with the glass composition of the second glass powder roughly the same.Thus, the affinity of the first seal, sealing materials film and the second seal, sealing materials film uprises, so the physical strength of seal, sealing materials layer improves.In addition, with regard to the first seal, sealing materials paste, the material beyond the granularity of preferred glass powder forms with the second seal, sealing materials paste roughly the same.Thus, the affinity of the first seal, sealing materials film and the second seal, sealing materials film further uprises.It should be noted that, in the situation that needs make the paste viscosity coupling of the first seal, sealing materials paste and the second seal, sealing materials paste, preferably the mixing ratio of seal, sealing materials and material containing is adjusted.
Seal, sealing materials paste (the first seal, sealing materials paste and the second seal, sealing materials paste) also preferably comprises the resistivity against fire filler.Thus, the physical strength of seal, sealing materials layer easily improves, and the thermal expansivity of seal, sealing materials layer easily reduces.
The median size D of resistivity against fire filler
50be 0.5 μ m～2.0 μ m, be particularly preferably 0.5 μ m～1.8 μ m.If the median size D of resistivity against fire filler
50too small, while burning till, the resistivity against fire filler easily is dissolved in glass, and softening the flowing of seal, sealing materials may be hindered.When this external pulverizing, classification, the easy aggegation of resistivity against fire filler, and remaining with the agglutinator form after seal, sealing materials paste mixing, when silk screen printing, may become screen plugging reason.On the other hand, if the median size D of resistivity against fire filler
50excessive, the concavo-convex excessive change of stacked film (particularly, the second seal, sealing materials film) is large during silk screen printing, and the surface smoothness of seal, sealing materials layer easily reduces.
As the resistivity against fire filler, can use zircon, zirconium white, stannic oxide, quartz, β-triphane, trichroite, mullite, silica glass, beta-eucryptite, β-quartz, zirconium phosphate, phosphoric acid wolframic acid zirconium, wolframic acid zirconium, NbZr (PO
4)
3deng there is [AB
2(MO
4)
3] essential structure compound,
A:Li, Na, K, Mg, Ca, Sr, Ba, Zn, Cu, Ni, Mn etc.
B:Zr, Ti, Sn, Nb, Al, Sc, Y etc.
M:P, Si, W, Mo etc.
Perhaps their sosoloid.
Seal, sealing materials paste (the first seal, sealing materials paste and the second seal, sealing materials paste) also preferably comprises pigment.Thus, the easy absorbing laser of seal, sealing materials layer.
Pigment optimization is mineral dye, more preferably selects white carbon, Co
3o
4, CuO, Cr
2o
3, Fe
2o
3, MnO
2, SnO, Ti
no
2n-1one or more in (n is integer), spinel system complex oxide, be particularly preferably carbon.These pigment are excellence aspect color developing, and the absorptivity of laser is good.As carbon, preferred amorphous carbon or graphite.These carbon have easily the median size D of primary particle
50be machined to the character of 1nm～100nm.It should be noted that, in use, contain Bi
2o
3the situation of glass powder under, from the viewpoint of suitability, consider, pigment optimization is one or more the oxide based pigment comprised in Cu, Cr, Fe, Mn.
The median size D of the primary particle of pigment
50be preferably 1nm～100nm, 3nm～70nm, 5nm～60nm, be particularly preferably 10nm～50nm.If the median size D of the primary particle of pigment
50too small, pigment easily aggegation each other, so pigment is difficult to disperse equably, during the laser sealing-in, the seal, sealing materials layer possibly can't soften mobile partly.On the other hand, even the median size D of the primary particle of pigment
50excessive, pigment also is difficult to disperse equably, and during the laser sealing-in, seal, sealing materials possibly can't soften mobile partly.
The content of the pigment in seal, sealing materials is 0.05 quality %～1 quality %, is particularly preferably 0.1 quality %～0.5 quality %.If the content of pigment is very few, be difficult to laser is converted to heat energy.On the other hand, if the content of pigment is too much, the seal, sealing materials layer is difficult to softening flowing during the laser sealing-in, is difficult in addition improve sealing strength.
From the environment viewpoint, consider, it is oxide compound that preferred pigments does not contain in fact Cr.
The softening temperature of seal, sealing materials is below 460 ℃, below 450 ℃, below 420 ℃, is particularly preferably below 400 ℃.If softening temperature is too high, the laser sealing-in easily reduces.The lower limit of softening temperature is not particularly limited, and still, if particularly consider the thermostability of glass powder, the softening temperature of preferred glass powder is more than 300 ℃.
Preferably that seal, sealing materials and material containing is mixing, and be processed into the seal, sealing materials paste.Thus, can improve coating workability etc.
Resin glue is aliphatic poly ethylene series carbonic ether, is particularly preferably polymerized thylene carbonate ethyl ester, poly (propylene carbonate).These resin glues have when unsticking mixture or laser sealing-in, and the glass powder that make glass powder, particularly contains SnO is difficult to rotten feature.
Solvent is preferably and selects white N, one or more in N '-dimethyl formamide, ethylene glycol, dimethyl sulfoxide (DMSO), methylcarbonate, Texacar PC, butyrolactone, caprolactone, METHYLPYRROLIDONE, diglycol monotertiary phenylate (PhDG), dibutyl phthalate (DBP), ethylene glycol monobenzyl ether (BzG), diglycol monotertiary benzyl oxide (BzDEG), ethyleneglycol monophenylether (PhG).These solvents have when unsticking mixture or laser sealing-in, the feature that the glass powder that make glass powder, particularly contains SnO is rotten.Particularly, in these solvents, be preferably one or more that select white Texacar PC, diglycol monotertiary phenylate (PhDG), dibutyl phthalate (DBP), ethylene glycol monobenzyl ether (BzG), diglycol monotertiary benzyl oxide (BzDEG), ethyleneglycol monophenylether (PhG).The boiling point of these solvents is more than 240 ℃.Therefore, if use these solvents,, when the coating operation of silk screen printing etc., easily suppress the volatilization of solvent, result is to use steadily in the long term the seal, sealing materials paste.And the affinity of diglycol monotertiary phenylate (PhDG), dibutyl phthalate (DBP), ethylene glycol monobenzyl ether (BzG), diglycol monotertiary benzyl oxide (BzDEG), ethyleneglycol monophenylether (PhG) and pigment is high.Therefore, even the addition of these solvents is a small amount of, also can suppress the situation that in the seal, sealing materials paste, pigment separates.
As mentioned above, Texacar PC, diglycol monotertiary phenylate (PhDG), dibutyl phthalate (DBP), ethylene glycol monobenzyl ether (BzG), diglycol monotertiary benzyl oxide (BzDEG), ethyleneglycol monophenylether (PhG) have the volatilization that suppresses solvent, improve the effect of the permanent stability of seal, sealing materials paste.
Seal, sealing materials film (the first seal, sealing materials film and the second seal, sealing materials film) is preferably processed, is particularly preferably supplied in N by the unsticking mixture in inert atmosphere
2unsticking mixture in atmosphere is processed.Thus, easily prevent when the unsticking mixture is processed glass powder, the rotten situation of glass powder that particularly contains SnO.
The seal, sealing materials layer preferably forms along the neighboring by the sealing-in thing, in the situation that be glass substrate by the sealing-in thing, preferably along the neighboring of glass substrate and form frame-like.Thus, but that the zone of receiving element becomes is large.
The surface roughness Ra of seal, sealing materials layer is below 0.6 μ m, below 0.5 μ m, is particularly preferably below 0.4 μ m.Thus, the seal, sealing materials layer with by the adaptation of sealing-in thing, improved, so laser sealing-in raising, and easily after the laser sealing-in, guarantee firm sealing strength.
The surfaceness RMS of seal, sealing materials layer is below 1.0 μ m, below 0.8 μ n, is particularly preferably below 0.7 μ m.Thus, the seal, sealing materials layer with by the adaptation of sealing-in thing, improved, so laser sealing-in raising, and easily after the laser sealing-in, guarantee firm sealing strength.
Next, the method for manufacturing electron device with the above this glass substrate with the seal, sealing materials layer is described.
At first, as shown in Figure 2 A, on the glass substrate 11 of forming element not, coating the first coating paste, form the first seal, sealing materials film 12.Now, the first seal, sealing materials paste is along the neighboring of glass substrate 11 and applied one-tenth frame-like.Next, as shown in Fig. 2 B, on the first seal, sealing materials film 12, coating the second seal, sealing materials paste, form the second seal, sealing materials film 13.Now, the second seal, sealing materials paste is along the applied one-tenth frame-like of the first seal, sealing materials film 12.In addition, make the coating width of the first seal, sealing materials paste and the second seal, sealing materials paste roughly the same.And, the median size D of the second glass powder in the second seal, sealing materials film 13
50median size D than the first glass powder in the first seal, sealing materials film 12
50thinner.Next, as shown in Figure 2 C, the stacked film of gained is burnt till, formed seal, sealing materials layer 14 on glass substrate 11.Seal, sealing materials layer 14 firmly is bonded on glass substrate 11.Then, make the surface of seal, sealing materials layer 14 become level and smooth.Finally, as shown in Figure 2 D, make to be formed with element and do not form the glass substrate 15 of seal, sealing materials layer to contact configuration with the glass substrate 1 with the seal, sealing materials layer, then carry out the laser sealing-in, make electron device.Now, from glass substrate 11 sides along seal, sealing materials layer 14 irradiating laser, glass substrate 1 and glass substrate 15 are by hermetic seal.Thus, can prevent the thermal degradation when of electronic device component, and the permanent stability of electron device improve.
The laser sealing-in is preferably carried out under inert atmosphere, particularly preferably in N
2carry out the laser sealing-in under atmosphere.Thus, easily prevent when laser sealing-in glass powder, the rotten situation of glass powder that particularly contains SnO.
The embodiment of the<the 2 related invention >
The manufacture method of the glass substrate with the seal, sealing materials layer that the embodiment of the 2nd related invention is related, it has following operation: (1) prepares the operation of glass substrate; (2) after coating the first seal, sealing materials paste, form the operation of the first seal, sealing materials film on described glass substrate; (3) be coated with the second seal, sealing materials paste on the first seal, sealing materials film, then form the operation of the second seal, sealing materials film; (4) stacked film of gained is burnt till, formed the operation of seal, sealing materials layer on glass substrate.
The first seal, sealing materials paste comprises the first glass powder, and comprises as required material containing, resistivity against fire filler, pigment.In addition, the second seal, sealing materials paste comprises the second glass powder, and comprises as required material containing, resistivity against fire filler, pigment.It is described that these compositions suitable is constructed as follows.It should be noted that, material containing comprises resin glue and solvent usually.
The softening temperature of the second glass powder is lower than the softening temperature of the first glass powder.The softening temperature of the second glass powder is preferably than low 5 ℃～50 ℃ of the softening temperature of the first glass powder, and the softening temperature of the second glass powder is more preferably than low 10 ℃～30 ℃ of the softening temperature of the first glass powder.If the softening temperature of the softening temperature of the second glass powder and the first glass powder is equal or higher, the surface smoothness of seal, sealing materials layer suffers damage, and is difficult to make the seal, sealing materials layer with closely sealed equably by the sealing-in thing, and the laser sealing-in easily reduces.It should be noted that, if the softening temperature of the second glass powder is more too low than the softening temperature of the first glass powder, the first seal, sealing materials paste is different from the behavior of the second seal, sealing materials paste, and the surface smoothness of seal, sealing materials layer may reduce on the contrary.
The softening temperature of the second glass powder is below 440 ℃, below 425 ℃, below 410 ℃, below 400 ℃, below 390 ℃, is particularly preferably 350～380 ℃.Thus, the surface smoothness of seal, sealing materials layer easily improves.It should be noted that, if the softening temperature of the second glass powder is too low, the easy devitrification of glass while burning till, in this case, the surface smoothness of seal, sealing materials layer may reduce on the contrary.In addition, the softening temperature of the first glass powder is below 450 ℃, below 435 ℃, below 410 ℃, below 400 ℃, is particularly preferably 360～390 ℃.Thus, easily improve the laser sealing-in.It should be noted that, if the softening temperature of the first glass powder is too low, the easy devitrification of glass while burning till, during the laser sealing-in, the seal, sealing materials layer is difficult to softening flowing.
The value of (density of the density of the second glass powder-first glass powder) is 0.01g/cm
3～0.50g/cm
3, be particularly preferably 0.05g/cm
3～0.40g/cm
3.Thus, the affinity of the first seal, sealing materials film and the second seal, sealing materials film uprises, so the physical strength of seal, sealing materials layer easily improves.
The value of (thermal expansivity of the thermal expansivity of the second glass powder-first glass powder) is 0.5 * 10
-7～10 * 10
-7/ ℃, be particularly preferably 1 * 10
-7～7 * 10
-7/ ℃.Thus, the softening temperature of the second glass powder is reduced, and easily prevent the situation that irrational stress is remaining at the seal, sealing materials layer.
In seal, sealing materials paste (the first seal, sealing materials paste and the second seal, sealing materials paste), the median size D of glass powder
50be 0.51 μ m～3.01 μ m, be particularly preferably 1.01 μ m～2.51 μ m.If the median size D of glass powder
50too small, the easy devitrification of glass while burning till, softening the flowing of seal, sealing materials may be hindered.In addition, pulverizing, during classification, the easy aggegation of glass powder, and remaining with the agglutinator form after seal, sealing materials paste mixing, thus screen plugging reason may be become when silk screen printing.On the other hand, if the median size D of glass powder
50excessive, the concavo-convex excessive change of seal, sealing materials film (wet film) is large during silk screen printing, the surface smoothness of seal, sealing materials layer easily reduces, and while burning till, the sealing-in material is difficult to softening flowing, therefore need to make firing temperature increase, in this case, by the thermal damage of sealing-in thing, easily become large, become the reason that cost raises.
In seal, sealing materials paste (the first seal, sealing materials paste and the second seal, sealing materials paste), 90% particle diameter D of glass powder
90be below 7.01 μ m, be particularly preferably below 5.0 μ m.Thus, easily make narrow and smallization of gap between glass substrate, in this case, the needed time shorten of laser sealing-in, even and the thermal expansivity of glass substrate and seal, sealing materials have difference, glass substrate, sealing-in part also is difficult to crack etc.
In seal, sealing materials paste (the first seal, sealing materials paste and the second seal, sealing materials paste), the maximum particle diameter D99 of glass powder is below 15 μ m, is particularly preferably below 10 μ m.Thus, easily make narrow and smallization of gap between glass substrate, in this case, the needed time shorten of laser sealing-in, even and the thermal expansivity of glass substrate and seal, sealing materials have difference, glass substrate, sealing-in part also is difficult to crack etc.
Glass powder (the first glass powder and the second glass powder) is preferably the glass powder that contains SnO, the glass powder that contains SnO forms mole expression % converted in following oxide compound as glass, preferably contain 35%～70% SnO, 10%～30% P
20
5.Below show the reason that is defined as above the glass compositing range.It should be noted that, in the explanation of glass compositing range, except the situation of specified otherwise, % means to refer to % by mole.
SnO is the composition that the glass eutectic is revealed.Its content is 35%～70%, 40%～70%, is particularly preferably 50%～68%.It should be noted that, as long as the content of SnO is more than 50%, during the laser sealing-in, glass is softening flowing easily.If the content of SnO is less than 35%, the viscosity of glass becomes too high, is difficult to use desirable laser output power to carry out the laser sealing-in.On the other hand, if the content of SnO, more than 70%, is difficult to vitrifying.
P
2o
5being network former, is the composition that improves thermostability.Its content is 10%～30%, 15%～27%, is particularly preferably 15%～25%.If P
2o
5content be less than 10%, thermostability easily reduces.On the other hand, if P
2o
5content more than 30%, weathering resistance reduces, and is difficult to guarantee the long-term reliability of organic EL device etc.
Except mentioned component, can also add following composition.
ZnO is intermidate oxide, and is the composition that makes stabilization.Its content is 0%～30%, 1%～20%, is particularly preferably 1%～15%.If the content of ZnO is more than 30%, thermostability easily reduces.
B
2o
3be network former, and be the composition that makes stabilization.In addition, B
2o
3it is the composition that improves weathering resistance.Its content is 0%～25%, 1%～20%, is particularly preferably 2%～15%.If B
2o
3content more than 20%, the viscosity of glass becomes too high, is difficult to use desirable laser output power to carry out the laser sealing-in.
Al
2o
3be intermidate oxide, and be the composition that makes stabilization.In addition, Al
2o
3it is the composition that thermal expansivity is reduced.Its content is 0%～10%, 0.1%～10%, is particularly preferably 0.5%～5%.If Al
2o
3content more than 10%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
SiO
2be network former, and be the composition that makes stabilization.Its content is 0%～15%, is particularly preferably 0%～5%.If SiO
2content more than 15%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
In
2o
3be the composition that improves thermostability, its content is preferably 0%～5%.If In
2o
3content more than 5%, job order cost is surging.
Ta
2o
5be the composition that improves thermostability, its content is preferably 0%～5%.If Ta
2o
5content more than 5%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
La
2o
3being the composition that improves thermostability, is the composition that improves weathering resistance in addition.Its content is preferably 0%～15%, 0%～10%, is particularly preferably 0%～5%.If La
2o
3content more than 15%, job order cost is surging.
MoO
3be the composition that improves thermostability, its content is preferably 0%～5%.If MoO
3content more than 5%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
WO
3be the composition that improves thermostability, its content is preferably 0%～5%.If WO
3content more than 5%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
Li
2o is the composition that the glass eutectic is revealed, and its content is preferably 0%～5%.If Li
2the content of O is more than 5%, and thermostability easily reduces.
Na
2o is the composition that the glass eutectic is revealed, and its content is 0%～10%, is particularly preferably 0%～5%.If Na
2the content of O is more than 10%, and thermostability easily reduces.
K
2o is the composition that the glass eutectic is revealed, and its content is preferably 0%～5%.If K
2the content of O is more than 5%, and thermostability easily reduces.
MgO is the composition that improves thermostability, and its content is preferably 0%～15%.If the content of MgO is more than 15%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
BaO is the composition that improves thermostability, and its content is preferably 0%～10%.If the content of BaO is more than 10%, the one-tenth balance-dividing that glass forms suffers damage, on the contrary the easy devitrification of glass.
F
2be the composition that the glass eutectic is revealed, its content is preferably 0%～5%.If F
2content more than 5%, thermostability easily reduces.
If consider thermostability and low melting point characteristic, In
2o
3, Ta
2o
5, La
2o
3, MoO
3, WO
3, Li
2o, Na
2o, K
2o, MgO, BaO, F
2total content be, below 10%, to be particularly preferably below 5%.
Except mentioned component, can also add for example to 10% of other compositions (CaO, SrO etc.).
With regard to the glass powder that contains SnO, preferably in forming, glass do not contain in fact transition metal oxide.Thus, easily improve thermostability.
Glass powder (the first glass powder and the second glass powder) is preferably Bi
2o
3-B
2o
3the glass frit end.Bi
2o
3-B
2o
3the glass frit end forms mole expression % converted in following oxide compound as glass, preferably contain 20%～60% Bi
2o
3, 10%～35% B
2o
3, 5%～40% ZnO, 5%～30% CuO+Fe
2o
3.Below show the reason that is defined as above the glass compositing range.It should be noted that, in the explanation of following glass compositing range, except the situation of specified otherwise, % means to refer to % by mole.
Bi
2o
3be the main component for reducing softening temperature, its content is 20%～60%, is preferably 25%～55%, more preferably 30%～55%.If Bi
2o
3content be less than 20%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.On the other hand, if Bi
2o
3content more than 60%, glass is to thermally labile, the easy devitrification of glass during melting or during the laser sealing-in.
B
2o
3be the composition that forms the glass network of bismuth glass, its content is 10～35%, is preferably 15～30%, more preferably 15～28%.If B
2o
3content be less than 10%, glass is to thermally labile, the easy devitrification of glass during melting or during the laser sealing-in.On the other hand, if B
2o
3content more than 35%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
ZnO is while controlling melting or the devitrification during laser sealing-in and the composition that thermal expansivity is reduced, and its content is 5%～40%, is preferably 5%～35%, more preferably 5%～33%.If the content of ZnO is less than 5%, be difficult to obtain above-mentioned effect.On the other hand, if the content of ZnO more than 40%, the one-tenth balance-dividing of glass in forming suffers damage, on the contrary the easy devitrification of glass.
CuO+Fe
2o
3be the composition with optical absorption characteristics, and be if irradiate the laser of the luminescence center wavelength with regulation, absorbing laser, make easily softening composition of glass.In addition, CuO+Fe
2o
3it is while suppressing melting or the composition of the devitrification during laser sealing-in.CuO+Fe
2o
3content be 5%～30%, be preferably 7%～25%, more preferably 10%～20%.If CuO+Fe
2o
3content be less than 5%, optical absorption characteristics deficiency, even irradiating laser, glass also is difficult to soften.On the other hand, if CuO+Fe
2o
3content more than 30%, the one-tenth balance-dividing in glass forms suffers damage, on the contrary the easy devitrification of glass.
CuO is the composition with optical absorption characteristics, if or irradiate the laser of the luminescence center wavelength with regulation, absorbing laser, make easily softening composition of glass, and be while suppressing melting or the composition of the devitrification during laser sealing-in.The content of CuO is preferably 0%～25%, 5%～25%, 10%～25%, and particularly 10%～20%.If the content of CuO is more than 25%, the one-tenth balance-dividing in the glass composition suffers damage, on the contrary the easy devitrification of glass.It should be noted that, as long as the content of CuO is restricted to more than 5%, optical absorption characteristics improves, and during the laser sealing-in, glass is easily softening.
Fe
2o
3the composition with optical absorption characteristics, if or irradiate the laser of the luminescence center wavelength with regulation, absorbing laser, make easily softening composition of glass, and be while suppressing melting or the composition of the devitrification during laser sealing-in.Fe
2o
3content be preferably 0%～10%, 0.1%～10%, 0.2%～10%, particularly 0.5%～10%.If Fe
2o
3content more than 10%, the one-tenth balance-dividing of glass in forming suffers damage, on the contrary the easy devitrification of glass.It should be noted that, as long as by Fe
2o
3content be limited in more than 0.1%, optical absorption characteristics improves, during the laser sealing-in, glass is easily softening.
The Fe ion comprised in glass is with Fe
2+or Fe
3+state exist.Fe ion in glass is not defined as Fe
2+or Fe
3+in a certain, and can be any one.Therefore, even at Fe
2+situation under, also can be scaled Fe
2o
3basis on processed.Particularly, in the situation that use infrared laser as irradiating light, Fe
2+there is absorption peak at region of ultra-red, therefore preferred Fe
2+ratio large, for example, preferably by the Fe in glass
2+/ Fe
3+proportional limit built in (being preferably more than 0.08) more than 0.03.
Except mentioned component, for example, can also add following composition.
SiO
2it is the composition that improves water tolerance.SiO
2content be preferably 0%～10%, particularly 0%～3%.If SiO
2content more than 10%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
Al
2o
3it is the composition that improves water tolerance.Al
2o
3content be preferably 0%～5%, particularly 0%～2%.If Al
2o
3content more than 5%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
The composition of the devitrification of MgO+CaO+SrO+BaO (the total content of MgO, CaO, SrO and BaO) when suppressing melting or during the laser sealing-in, the content of MgO+CaO+SrO+BaO is preferably 0%～20%, and particularly 0%～15%.If the content of MgO+CaO+SrO+BaO is more than 20%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
MgO, CaO and SrO are while suppressing melting or the composition of the devitrification during laser sealing-in.The content of each composition is preferably 0%～5%, and particularly 0%～2%.If the content of each composition is more than 5%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
BaO is while suppressing melting or the composition of the devitrification during laser sealing-in.The content of BaO is preferably 0%～15%, and particularly 0%～10%.If the content of BaO is more than 15%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
CeO
2and Sb
2o
3it is while suppressing melting or the composition of the devitrification during laser sealing-in.The content of each composition is preferably 0%～5%, 0%～2%, and particularly 0%～1%.If the content of each composition is more than 5%, the one-tenth balance-dividing in the glass composition suffers damage, on the contrary the easy devitrification of glass.It should be noted that, consider from the viewpoint that improves thermostability, preferably Sb
2o
3for indium addition, particularly, preferably add the Sb more than 0.05%
2o
3.
WO
3it is while suppressing melting or the composition of the devitrification during laser sealing-in.WO
3content be preferably 0%～10%, particularly 0%～2%.If WO
3content more than 10%, the one-tenth balance-dividing of glass in forming suffers damage, on the contrary the easy devitrification of glass.
In
2o
3+ Ga
2o
3(In
2o
3with Ga
2o
3total content) be while suppressing melting or the composition of the devitrification during laser sealing-in.In
2o
3+ Ga
2o
3content be preferably 0%～5%, particularly 0～3%.If In
2o
3+ Ga
2o
3content more than 5%, job order cost is surging.It should be noted that In
2o
3content more preferably 0%～1%, Ga
2o
3content more preferably 0%～0.5%.
The oxide compound of Li, Na, K and Cs is the composition that softening temperature is reduced, and promotes the effect of devitrification owing to having melting, therefore preferably to add up to content meter, is restricted to and is less than 1%.
P
2o
5it is the composition of the devitrification while suppressing melting.But, if P
2o
5content more than 1%, the easy phase-splitting of glass during melting.
La
2o
3, Y
2o
3and Gd
2o
3be the composition of the phase-splitting while suppressing melting, if these add up to content more than 3%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
NiO, V
2o
5, CoO, MoO
3, TiO
2and MnO
2be the composition with optical absorption characteristics, and be if irradiate the laser of the luminescence center wavelength with regulation, absorbing laser, make easily softening composition of glass.The content of each composition is preferably 0%～7%, and particularly 0%～3%.If the content of each composition is more than 7%, the easy devitrification of glass during the laser sealing-in.
PbO is the composition that softening temperature is reduced, but is also possible to environment, bring the composition of impact.Therefore, the content of PbO preferably is less than 0.1%.
For example, even the composition beyond above-mentioned, also can, in the scope of not damaging glass performance, be added into 5%.
With regard to glass powder (the first glass powder and the second glass powder), from the environment viewpoint, consider, preferably in forming, glass do not contain in fact PbO.
Seal, sealing materials paste (the first seal, sealing materials paste and the second seal, sealing materials paste) also preferably comprises the resistivity against fire filler.Thus, the physical strength of seal, sealing materials layer easily improves, and the thermal expansivity of seal, sealing materials layer easily reduces.
The median size D of resistivity against fire filler
50be 0.5 μ m～2.0 μ m, be particularly preferably 0.5 μ m～1.8 μ m.If the median size D of resistivity against fire filler
50too small, while burning till, the resistivity against fire filler easily dissolves in glass, and softening the flowing of seal, sealing materials may be hindered.In addition, pulverizing, during classification, the easy aggegation of resistivity against fire filler, remaining with the agglutinator form after seal, sealing materials paste mixing, when silk screen printing, may become screen plugging reason.On the other hand, if the median size D of resistivity against fire filler
50excessive, the concavo-convex of stacked film (particularly, the second seal, sealing materials film) becomes excessive during silk screen printing, and the surface smoothness of seal, sealing materials layer easily reduces.
As the resistivity against fire filler, can use zircon, zirconium white, stannic oxide, quartz, β-triphane, trichroite, mullite, silica glass, beta-eucryptite, β-quartz, zirconium phosphate, phosphoric acid wolframic acid zirconium, wolframic acid zirconium, NbZr (PO
4)
3deng there is [AB
2(MO
4)
3] essential structure compound,
A:Li, Na, K, Mg, Ca, Sr, Ba, Zn, Cu, Ni, Mn etc.
B:Zr, Ti, Sn, Nb, Al, Sc, Y etc.
M:P, Si, W, Mo etc.
Perhaps their sosoloid.
Seal, sealing materials paste (the first seal, sealing materials paste and the second seal, sealing materials paste) also preferably comprises pigment.Thus, the easy absorbing laser of seal, sealing materials layer.
Pigment optimization is mineral dye, more preferably selects white carbon, Co
3o
4, CuO, Cr
2o
3, Fe
2o
3, MnO
2, SnO, Ti
no
2n-1one or more in (n is integer), spinel system complex oxide, being particularly preferably is carbon.These pigment are excellence aspect color developing, and the absorptivity of laser is good.As carbon, preferred amorphous carbon or graphite.These carbon have easily the median size D of primary particle
50be machined to the character of 1～100nm.It should be noted that, as glass powder, in use, contain Bi
2o
3the situation of glass powder under, from the viewpoint of suitability, consider, pigment optimization is one or more the oxide based pigment comprised in Cu, Cr, Fe, Mn.
The median size D of the primary particle of pigment
50for 1nm～100nm, 3nm～70nm, 5nm～60nm, be particularly preferably 10nm～50nm.If the median size D of the primary particle of pigment
50too small, pigment is with the easy aggegation of scholar, so pigment is difficult to dispersedly, and during the laser sealing-in, the seal, sealing materials layer possibly can't soften mobile partly.On the other hand, even the median size D of the primary particle of pigment
50excessive, pigment also is difficult to disperse equably, and during the laser sealing-in, seal, sealing materials possibly can't soften mobile partly.
The content of the pigment in seal, sealing materials is 0.05 quality %～1 quality %, is particularly preferably 0.1 quality %～0.5 quality %.If the content of pigment is very few, be difficult to laser is converted to heat energy.On the other hand, if the content of pigment is too much, the seal, sealing materials layer is difficult to softening flowing during the laser sealing-in, is difficult in addition improve sealing strength.
From the environment viewpoint, consider, it is oxide compound that pigment optimization does not contain in fact Cr.
The softening temperature of seal, sealing materials is below 460 ℃, below 450 ℃, below 420 ℃, is particularly preferably below 400 ℃.If softening temperature is too high, the laser sealing-in easily reduces.Although be not particularly limited the lower limit of softening temperature, if consider the thermostability of glass powder, particularly glass powder, softening temperature is preferably more than 350 ℃.
Preferably that seal, sealing materials and material containing is mixing, and be processed into the seal, sealing materials paste.Thus, can improve coating workability etc.
Resin glue is aliphatic poly ethylene series carbonic ether, is particularly preferably polymerized thylene carbonate ethyl ester, poly (propylene carbonate).These resin glues have when unsticking mixture or laser sealing-in, and the glass powder that make glass powder, particularly contains SnO is difficult to rotten feature.
Solvent is preferably and selects white N, one or more in N '-dimethyl formamide, ethylene glycol, dimethyl sulfoxide (DMSO), methylcarbonate, Texacar PC, butyrolactone, caprolactone, METHYLPYRROLIDONE, diglycol monotertiary phenylate (PhDG), dibutyl phthalate (DBP), ethylene glycol monobenzyl ether (BzG), diglycol monotertiary benzyl oxide (BzDEG), ethyleneglycol monophenylether (PhG).These solvents have when unsticking mixture or laser sealing-in, the feature that the glass powder that make glass powder, particularly contains SnO is rotten.Particularly, in these solvents, be preferably and select one or more in white Texacar PC, diglycol monotertiary phenylate (PhDG), dibutyl phthalate (DBP), ethylene glycol monobenzyl ether (BzG), diglycol monotertiary benzyl oxide (BzDEG), ethyleneglycol monophenylether (PhG).The boiling point of these solvents is more than 240 ℃.Therefore, if use these solvents,, when the coating operation of silk screen printing etc., easily suppress the volatilization of solvent, result is can the low seal, sealing materials paste that uses steady in a long-term.And the affinity of diglycol monotertiary phenylate (PhDG), dibutyl phthalate (DBP), ethylene glycol monobenzyl ether (BzG), diglycol monotertiary benzyl oxide (BzDEG), ethyleneglycol monophenylether (PhG) and pigment is high.Therefore, even the addition of these dissolvings is a small amount of, also can suppress the situation that in the seal, sealing materials paste, pigment separates.
As mentioned above, Texacar PC, diglycol monotertiary phenylate (PhDG), dibutyl phthalate (DBP), ethylene glycol monobenzyl ether (BzG), diglycol monotertiary benzyl oxide (BzDEG), ethyleneglycol monophenylether (PhG) have the volatilization that suppresses solvent, improve the effect of the permanent stability of seal, sealing materials paste.
Seal, sealing materials film (the first seal, sealing materials film and the second seal, sealing materials film) is preferably processed by the unsticking mixture in inert atmosphere, is particularly preferably supplied in N
2unsticking mixture in atmosphere is processed.Thus, easily prevent when unsticking mixture glass powder, the rotten situation of glass powder that particularly contains SnO.
The seal, sealing materials layer preferably forms along the neighboring by the sealing-in thing, in the situation that be glass substrate by the sealing-in thing, preferably along the neighboring of glass substrate and form frame-like.Thus, the zone that can accommodate element becomes large.
The surface roughness Ra of seal, sealing materials layer is below 0.6 μ m, below 0.5 μ m, is particularly preferably below 0.4 μ m.Thus, the seal, sealing materials layer with by the adaptation of sealing-in thing, improved, so laser sealing-in raising, and easily after the laser sealing-in, guarantee firm sealing strength.
The surfaceness RMS of seal, sealing materials layer is below 1.0 μ m, below 0.8 μ m, is particularly preferably below 0.7 μ m.Thus, the seal, sealing materials layer with by the adaptation of sealing-in thing, improved, so laser sealing-in raising, and easily after the laser sealing-in, guarantee firm sealing strength.
Next, to having used the manufacture method above-mentioned glass substrate with the seal, sealing materials layer, electron device to describe.It should be noted that therefore the part that the manufacture method of the electron device illustrated in the embodiment due to existence and the 1st related invention is common is directly used Fig. 2 A～D and described.
That is, at first, as shown in Figure 2 A, on the glass substrate 11 of forming element not, coating the first coating paste, form the first seal, sealing materials film 12.Now, the first seal, sealing materials paste is along the neighboring of glass substrate 11 and applied one-tenth frame-like.Next, as shown in Fig. 2 B, on the first seal, sealing materials film 12, coating the second seal, sealing materials paste, form the second seal, sealing materials film 13.Now, the second seal, sealing materials paste is along the applied one-tenth frame-like of the first seal, sealing materials film 12.In addition, make the coating width of the first seal, sealing materials paste and the second seal, sealing materials paste roughly the same.And, make the softening temperature of the softening temperature of the glass powder in the second seal, sealing materials film 13 lower than the glass powder in the first seal, sealing materials film 12.Next, as shown in Figure 2 C, the stacked film of gained is burnt till, formed seal, sealing materials layer 14 on glass substrate 11.Seal, sealing materials layer 14 firmly is bonded on glass substrate 11.Then, make the surface of seal, sealing materials layer 14 become level and smooth.Finally, as shown in Figure 2 D, make to be formed with element and do not form the glass substrate 15 of seal, sealing materials layer to contact configuration with the glass substrate 1 with the seal, sealing materials layer, then carry out the laser sealing-in, make electron device.Now, from glass substrate 11 sides along seal, sealing materials layer 14 irradiating laser, glass substrate 1 and glass substrate 15 are by hermetic seal.Thus, can prevent the thermal degradation when of electronic device component, and the permanent stability of electron device improve.
The laser sealing-in is preferably carried out under inert atmosphere, particularly preferably in N
2carry out the laser sealing-in under atmosphere.Thus, easily prevent when laser sealing-in glass powder, the rotten situation of glass powder that particularly contains SnO.
The embodiment of the<the 3 related invention >
The manufacture method of the glass substrate with the seal, sealing materials layer that the embodiment of the 3rd related invention is related, it has following operation: (1) prepares the operation of glass substrate; (2) be coated with the first seal, sealing materials paste on described glass substrate, then form the operation of the first seal, sealing materials film; (3) be coated with the second seal, sealing materials paste on the first seal, sealing materials film, then form the operation of the second seal, sealing materials film; (4) stacked film of gained is burnt till, formed the operation of seal, sealing materials layer on glass substrate.
The first seal, sealing materials paste at least comprises the first seal, sealing materials, usually, also comprises material containing.The first seal, sealing materials at least comprises the resistivity against fire filler, usually, also comprises glass powder and pigment.The second seal, sealing materials paste at least comprises the second seal, sealing materials, usually, also comprises material containing.The second seal, sealing materials at least comprises the resistivity against fire filler, usually, also comprises glass powder and pigment.It should be noted that, as glass powder, can use various glass powders, but as described later, preferably contain the glass powder of SnO or contain Bi
20
3glass powder.The material after resin glue is dissolved in solvent is normally instigated in material containing, as required, preferably also adds tensio-active agent etc.
It is described that these compositions suitable is constructed as follows.
The content of the resistivity against fire filler in the second seal, sealing materials (wherein, remove the content of pigment and calculate) is 5 volume %～40 volume %, is particularly preferably 10 volume %～35 volume %.If the content of resistivity against fire filler is very few, with the difference of for example, thermal expansivity by sealing-in thing (not forming the glass substrate of seal, sealing materials layer) or the first seal, sealing materials, become large, thereby crackle etc. occurs, therefore be difficult to guarantee resistance to air loss.In addition, will be difficult to enjoy effect, the effect that reduces thermal expansivity produced by the resistivity against fire filler, the effect that physical strength is improved etc.On the other hand, if the content of resistivity against fire filler is too much, softening the flowing of the second seal, sealing materials hindered, and the surface smoothness of seal, sealing materials layer easily reduces.Consequently, the laser sealing-in easily reduces.
The content of the resistivity against fire filler in the first seal, sealing materials (wherein, remove the content of pigment and calculate) is 20 volume %～60 volume %, is particularly preferably 30 volume %～50 volume %.If the content of resistivity against fire filler is very few, with the difference of for example, thermal expansivity by sealing-in thing (not forming the glass substrate of seal, sealing materials layer), become large, thereby crackle etc. occurs, therefore be difficult to guarantee resistance to air loss.In addition, will be difficult to enjoy effect, the effect that reduces thermal expansivity produced by the resistivity against fire filler, the effect that physical strength is improved etc.On the other hand, if the content of resistivity against fire filler is too much, softening the flowing of the first seal, sealing materials may be hindered.In addition, become large with the difference of the thermal expansivity of the second seal, sealing materials, thereby crackle etc. occurs, therefore be difficult to guarantee resistance to air loss.
The median size D of resistivity against fire filler
50be 0.5 μ m～2.0 μ m, be particularly preferably 0.5 μ m～1.8 μ m.If the median size D of resistivity against fire filler
50too small, while burning till, the resistivity against fire filler easily dissolves in glass, and softening the flowing of seal, sealing materials may be hindered.In addition, pulverizing, during classification, the easy aggegation of resistivity against fire filler, remaining with the agglutinator form after seal, sealing materials paste mixing, when silk screen printing, may become screen plugging reason.On the other hand, if the median size D of resistivity against fire filler
50excessive, the concavo-convex of stacked film (particularly, the second seal, sealing materials film) becomes excessive during silk screen printing, and the surface smoothness of seal, sealing materials layer easily reduces.
As the resistivity against fire filler, can use zircon, zirconium white, stannic oxide, quartz, β-triphane, trichroite, mullite, silica glass, beta-eucryptite, β-quartz, zirconium phosphate, phosphoric acid wolframic acid zirconium, wolframic acid zirconium, NbZr (PO
4)
3deng there is [AB
2(MO
4)
3] essential structure compound,
A:Li, Na, K, Mg, Ca, Sr, Ba, Zn, Cu, Ni, Mn etc.
B:Zr, Ti, Sn, Nb, Al, Sc, Y etc.
M:P, Si, W, Mo etc.
Perhaps their sosoloid.
The value of (thermal expansivity of the thermal expansivity of the second seal, sealing materials-first seal, sealing materials) is 1 * 10
-7/ ℃～45 * 10
-7/ ℃, be particularly preferably 8 * 10
-7/ ℃～28 * 10
-7/ ℃.Thus, when promoting the second seal, sealing materials softening mobile, easily prevent that irrational stress from remaining in the situation of seal, sealing materials layer.
In seal, sealing materials (the first seal, sealing materials and the second seal, sealing materials), the median size D of glass powder
50be 1.0 μ m～3.0 μ m, be particularly preferably 1.5 μ m～2.5 μ m.If the median size D of glass powder
50too small, the easy devitrification of glass while burning till, softening the flowing of seal, sealing materials may be hindered.In addition, pulverizing, during classification, the easy aggegation of glass powder, remaining with the agglutinator form after seal, sealing materials paste mixing, may become screen plugging reason when silk screen printing.On the other hand, if the median size D of glass powder
50excessive, the concavo-convex of seal, sealing materials film (wet film) becomes excessive during silk screen printing, the surface smoothness of seal, sealing materials layer easily reduces, and seal, sealing materials is difficult to softening flowing when burning till, therefore need to make firing temperature increase, in this case, by the thermal damage of sealing-in thing, easily become large, can become the reason that cost raises." median size D
50" referring to the value of measuring by laser diffractometry, while meaning to measure by laser diffractometry, in the cumulative grain-size distribution curve of volume reference, the side that its semi-invariant is little from particle starts to accumulate and is 50% particle diameter.
In seal, sealing materials (the first seal, sealing materials and the second seal, sealing materials), 90% particle diameter D of glass powder
90be below 7.0 μ m, be particularly preferably below 5.0 μ m.Thus, easily make narrow and smallization of gap between glass substrate, in this case, the needed time shorten of laser sealing-in, even and the thermal expansivity of glass substrate and seal, sealing materials have difference, glass substrate, sealing-in part also is difficult to occur crackle etc.
In seal, sealing materials (the first seal, sealing materials and the second seal, sealing materials), the maximum particle diameter D of glass powder
99be below 15 μ m, be particularly preferably below 10 μ m.Thus, easily make narrow and smallization of gap between glass substrate, in this case, the needed time shorten of laser sealing-in, even and the thermal expansivity of glass substrate and seal, sealing materials have difference, glass substrate, sealing-in part also is difficult to occur crackle etc.
Glass powder is preferably the glass powder that contains SnO, and the glass powder that contains SnO forms mole expression % converted in following oxide compound as glass, preferably contain 35%～70% SnO, 10%～30% P
2o
5.Below show the reason that is defined as above the glass compositing range.It should be noted that, in the explanation of glass compositing range, except the situation of specified otherwise, % means to refer to % by mole.
SnO is the composition that the glass eutectic is revealed.Its content is 35%～70%, 40%～70%, is particularly preferably 50%～68%.It should be noted that, as long as the content of SnO is more than 50%, during the laser sealing-in, glass is softening flowing easily.If the content of SnO is less than 35%, the viscosity of glass becomes too high, is difficult to use desirable laser output power to carry out the laser sealing-in.On the other hand, if the content of SnO, more than 70%, is difficult to vitrifying.
P
2o
5be network former, and be the composition that improves thermostability.Its content is 10%～30%, 15%～27%, is particularly preferably 15%～25%.If P
2o
5content be less than 10%, thermostability easily reduces.On the other hand, if P
2o
5content more than 30%, weathering resistance reduces, and is difficult to guarantee the long-term reliability of organic EL device etc.
Except mentioned component, can also add following composition.
ZnO is intermidate oxide, and is the composition that makes stabilization.Its content is 0%～30%, 1%～20%, is particularly preferably 1%～15%.If the content of ZnO is more than 30%, thermostability easily reduces.
B
2o
3be network former, and be the composition that makes stabilization.In addition, B
2o
3it is the composition that improves weathering resistance.Its content is 0%～25%, 1%～20%, is particularly preferably 2%～15%.If B
2o
3content more than 20%, viscosity becomes too high, is difficult to use desirable laser output power to carry out the laser sealing-in.
Al
2o
3be intermidate oxide, and be the composition that makes stabilization.In addition, Al
2o
3it is the composition that thermal expansivity is reduced.Its content is 0%～10%, 0.1%～10%, is particularly preferably 0.5%～5%.If Al
2o
3content more than 10%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
SiO
2be network former, and be the composition that makes stabilization.Its content is 0%～15%, is particularly preferably 0%～5%.If SiO
2content more than 15%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
In
2o
3be the composition that improves thermostability, its content is preferably 0%～5%.If In
2o
3content more than 5%, job order cost is surging.
Ta
2o
5be the composition that improves thermostability, its content is preferably 0～5%.If Ta
2o
5content more than 5%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
La
2o
3being the composition that improves thermostability, is the composition that improves weathering resistance in addition.Its content is 0%～15%, 0%～10%, is particularly preferably 0%～5%.If La
2o
3content more than 15%, job order cost is surging.
MoO
3be the composition that improves thermostability, its content is preferably 0%～5%.If MoO
3content more than 5%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
WO
3be the composition that improves thermostability, its content is preferably 0%～5%.If WO
3content more than 5%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
Li
2o is the composition that the glass eutectic is revealed, and its content is preferably 0%～5%.If Li
2the content of O is more than 5%, and thermostability easily reduces.
Na
2o is the composition that the glass eutectic is revealed, and its content is 0%～10%, is particularly preferably 0%～5%.If Na
2the content of O is more than 10%, and thermostability easily reduces.
K
2o is the composition that the glass eutectic is revealed, and its content is preferably 0%～5%.If K
2the content of O is more than 5%, and thermostability easily reduces.
MgO is the composition that improves thermostability, and its content is preferably 0～15%.If the content of MgO is more than 15%, the softening temperature of glass powder rises undeservedly, is difficult to use desirable laser output power to carry out the laser sealing-in.
BaO is the composition that improves thermostability, and its content is preferably 0%～10%.If the content of BaO is more than 10%, the one-tenth balance-dividing that glass forms suffers damage, on the contrary the easy devitrification of glass.
F
2be the composition that the glass eutectic is revealed, its content is preferably 0%～5%.If F
2content more than 5%, thermostability easily reduces.
If consider thermostability and low melting point characteristic, In
2o
3, Ta
2o
5, La
2o
3, MoO
3, WO
3, Li
2o, Na
2o, K
2o, MgO, BaO, F
2total content be, below 10%, to be particularly preferably below 5%.
Except mentioned component, also can add for example to 10% of other compositions (CaO, SrO etc.).
With regard to the glass powder that contains SnO, preferred glass does not comprise in fact transition metal oxide in forming.Thus, easily improve thermostability.
Glass powder (the first glass powder and the second glass powder) also is preferably Bi
2o
3-B
2o
3the glass frit end.Bi
2o
3-B
2o
3the glass frit end forms mole expression % converted in following oxide compound as glass, preferably contain 20%～60% Bi
2o
3, 10%～35% B
2o
3, 5%～40% ZnO, 5%～30% CuO+Fe
2o
3.Below show the reason that is defined as above the glass compositing range.It should be noted that, in the explanation of following glass compositing range, except the situation of specified otherwise, % means to refer to % by mole.
Bi
2o
3be the main component for reducing softening temperature, its content is 20%～60%, is preferably 25%～55%, more preferably 30%～55%.If Bi
2o
3content be less than 20%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.On the other hand, if Bi
2o
3content more than 60%, glass is to thermally labile, the easy devitrification of glass during melting or during the laser sealing-in.
B
2o
3be the composition that forms the glass network of bismuth glass, its content is 10%～35%, is preferably 15%～30%, more preferably 15%～28%.If B
2o
3content be less than 10%, glass is to thermally labile, the easy devitrification of glass during melting or during the laser sealing-in.On the other hand, B
2o
3if content more than 35%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
ZnO is while suppressing melting or the devitrification during laser sealing-in, and the composition that thermal expansivity is reduced, and its content is 5%～40%, is preferably 5%～35%, more preferably 5%～33%.If the content of ZnO is less than 5%, be difficult to obtain above-mentioned effect.On the other hand, if the content of ZnO more than 40%, the one-tenth balance-dividing of glass in forming suffers damage, on the contrary the easy devitrification of glass.
CuO+Fe
2o
3be the composition with optical absorption characteristics, and be if irradiate the laser of the luminescence center wavelength with regulation, absorbing laser, make easily softening composition of glass.In addition, CuO+Fe
2o
3it is while suppressing melting or the composition of the devitrification during laser sealing-in.CuO+Fe
2o
3content be 5%～30%, be preferably 7%～25%, more preferably 10%～20%.If CuO+Fe
2o
3content be less than 5%, optical absorption characteristics deficiency, even irradiating laser, glass also is difficult to soften.On the other hand, if CuO+Fe
2o
3content more than 30%, the one-tenth balance-dividing of glass in forming suffers damage, on the contrary the easy devitrification of glass.
CuO is the composition with optical absorption characteristics, if or irradiate the laser of the luminescence center wavelength with regulation, absorbing laser, make easily softening composition of glass, and be while suppressing melting or the composition of the devitrification during laser sealing-in.The content of CuO is preferably 0%～25%, 5%～25%, 10%～25%, and particularly 10%～20%.If the content of CuO is more than 25%, the one-tenth balance-dividing in the glass composition suffers damage, on the contrary the easy devitrification of glass.It should be noted that, as long as the content of CuO is limited in more than 5%, optical absorption characteristics improves, and during the laser sealing-in, glass is easily softening.
Fe
2o
3the composition with optical absorption characteristics, if or irradiate the laser of the luminescence center wavelength with regulation, absorbing laser, make easily softening composition of glass, and be while suppressing melting or the composition of the devitrification during laser sealing-in.Fe
2o
3content be preferably 0%～10%, 0.1%～10%, 0.2%～10%, particularly 0.5%～10%.If Fe
2o
3content more than 10%, the one-tenth balance-dividing of glass in forming suffers damage, on the contrary the easy devitrification of glass.It should be noted that, as long as by Fe
2o
3content be limited in more than 0.1%, optical absorption characteristics improves, during the laser sealing-in, glass is easily softening.
The Fe ion comprised in glass is with Fe
2+or Fe
3+state exist.Fe ion in glass is not defined as Fe
2+or Fe
3+in a certain, and can be any one.Therefore, even at Fe
2+situation under, also can be scaled Fe
2o
3basis on processed.Particularly, in the situation that use infrared laser as irradiating light, Fe
2+there is absorption peak at region of ultra-red, therefore preferred Fe
2+ratio large, for example, preferably by the Fe in glass
2+/ Fe
3+proportional limit built in (being preferably more than 0.08) more than 0.03.
Except mentioned component, for example, can also add following composition.
SiO
2it is the composition that improves water tolerance.SiO
2content be preferably 0%～10%, particularly 0%～3%.If SiO
2content more than 10%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
Al
2o
3it is the composition that improves water tolerance.Al
2o
3content be preferably 0%～5%, particularly 0%～2%.If Al
2o
3content more than 5%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
MgO+CaO+SrO+BaO (the total content of MgO, CaO, SrO and BaO) is while suppressing melting or the composition of the devitrification during laser sealing-in, and the content of MgO+CaO+SrO+BaO is preferably 0%～20%, particularly 0%～15%.If the content of MgO+CaO+SrO+BaO is more than 20%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
MgO, CaO and SrO are while suppressing melting or the composition of the devitrification during laser sealing-in.The content of each composition is preferably 0%～5%, and particularly 0%～2%.If the content of each composition is more than 5%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
BaO is while suppressing melting or the composition of the devitrification during laser sealing-in.The content of BaO is preferably 0%～15%, and particularly 0%～10%.If the content of BaO is more than 15%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
CeO
2and Sb
2o
3it is while suppressing melting or the composition of the devitrification during laser sealing-in.The content of each composition is preferably 0%～5%, 0%～2%, and particularly 0%～1%.If the content of each composition is more than 5%, the one-tenth balance-dividing in the glass composition suffers damage, on the contrary the easy devitrification of glass.It should be noted that, consider from the viewpoint that improves thermostability, preferably Sb
2o
3for indium addition, particularly, preferably add the Sb more than 0.05%
2o
3.
WO
3it is while suppressing melting or the composition of the devitrification during laser sealing-in.WO
3content be preferably 0%～10%, particularly 0%～2%.If WO
3content more than 10%, the one-tenth balance-dividing of glass in forming suffers damage, on the contrary the easy devitrification of glass.
In
2o
3+ Ga
2o
3(In
2o
3and Ga
2o
3total content) be while suppressing melting or the composition of the devitrification during laser sealing-in.In
2o
3+ Ga
2o
3content be preferably 0%～5%, particularly 0%～3%.If In
2o
3+ Ga
2o
3content more than 5%, job order cost is surging.It should be noted that In
2o
3content more preferably 0%～1%, Ga
2o
3content more preferably 0%～0.5%.
The oxide compound of Li, Na, K and Cs is the composition that softening temperature is reduced, and promotes the effect of devitrification while having melting, therefore preferably to add up to content meter, is restricted to and is less than 1%.
P
2o
5it is the composition of the devitrification while suppressing melting.But, if P
2o
5content more than 1%, the easy phase-splitting of glass during melting.
La
2o
3, Y
2o
3and Gd
2o
3the composition of the phase-splitting while suppressing melting, if the total content of these compositions more than 3%, softening temperature becomes too high, even irradiating laser, glass also is difficult to soften.
NiO, V
2o
5, CoO, MoO
3, TiO
2and MnO
2be the composition with optical absorption characteristics, and be if irradiate the laser of the luminescence center wavelength with regulation, absorbing laser, make easily softening composition of glass.The content of each composition is preferably 0%～7%, and particularly 0%～3%.If the content of each composition is more than 7%, the easy devitrification of glass during the laser sealing-in.
PbO is the composition that softening temperature is reduced, and is possible to environment, bring the composition of impact.Therefore, the content of PbO is preferably and is less than 0.1%.
For example, even the composition beyond above-mentioned, also can, in the scope of not damaging glass performance, be added into 5%.
From the environment viewpoint, consider, glass powder (the first glass powder and the second glass powder) does not preferably contain in fact PbO in glass forms.
Seal, sealing materials paste (the first seal, sealing materials paste and the second seal, sealing materials paste) also preferably comprises pigment.Thus, the easy absorbing laser of seal, sealing materials layer.
Pigment optimization is mineral dye, more preferably selects white carbon, Co
3o
4, CuO, Cr
2o
3, Fe
2o
3, MnO
2, SnO, Ti
no
2n-1one or more in (n is integer), spinel system complex oxide, be particularly preferably carbon.These pigment are excellence aspect color developing, and the absorptivity of laser is good.As carbon, preferred amorphous carbon or graphite.These carbon have the median size D of primary particle
50be machined to the character of 1nm～100nm.It should be noted that, as glass powder, in use, contain Bi
2o
3the situation of glass powder under, the viewpoint of suitability considers, pigment optimization is one or more the oxide based pigment comprised in Cu, Cr, Fe, Mn.
The median size D of the primary particle of pigment
50be preferably 1nm～100nm, 3nm～70nm, 5nm～60nm, be particularly preferably 10nm～50nm.If the median size D of the primary particle of pigment
50too small, pigment easily aggegation each other, so pigment is difficult to disperse equably, during the laser sealing-in, the seal, sealing materials layer possibly can't soften mobile partly.On the other hand, even the median size D of the primary particle of pigment
50excessive, pigment also is difficult to disperse equably, and during the laser sealing-in, seal, sealing materials may soften mobile in institute of office ground.
The content of the pigment in seal, sealing materials (the first seal, sealing materials and the second seal, sealing materials) is 0.05 quality %～1 quality %, is particularly preferably 0.1 quality %～0.5 quality %.If the content of pigment is very few, be difficult to laser is converted to heat energy.On the other hand, if the content of pigment is too much, the seal, sealing materials layer is difficult to softening flowing during the laser sealing-in, is difficult in addition improve sealing strength.
From the environment viewpoint, consider, it is oxide compound that preferred pigments does not contain in fact Cr.
In seal, sealing materials (the first seal, sealing materials and the second seal, sealing materials), softening temperature is below 450 ℃, below 420 ℃, is particularly preferably below 400 ℃.If softening temperature is too high, the laser sealing-in easily reduces.The lower limit of softening temperature is not particularly limited, if but consider glass powder, the thermostability of the glass powder that particularly contains SnO, softening temperature is preferably more than 350 ℃.
The first seal, sealing materials and material containing be by mixing, and then be processed to the first seal, sealing materials paste.In addition, the second seal, sealing materials and material containing be by mixing, and then be processed to the second seal, sealing materials paste.Thus, can improve coating workability etc.
Resin glue is aliphatic poly ethylene series carbonic ether, is particularly preferably polymerized thylene carbonate ethyl ester, poly (propylene carbonate).These resin glues have when unsticking mixture or laser sealing-in, and the glass powder that make glass powder, particularly contains SnO is difficult to rotten feature.
Solvent is preferably and selects white N, one or more in N '-dimethyl formamide, ethylene glycol, dimethyl sulfoxide (DMSO), methylcarbonate, Texacar PC, butyrolactone, caprolactone, METHYLPYRROLIDONE, diglycol monotertiary phenylate (PhDG), dibutyl phthalate (DBP), ethylene glycol monobenzyl ether (BzG), diglycol monotertiary benzyl oxide (BzDEG), ethyleneglycol monophenylether (PhG).These solvents have when unsticking mixture or laser sealing-in, and the glass powder that make glass powder, particularly contains SnO is difficult to rotten feature.Particularly, in these solvents, be preferably and select one or more in white Texacar PC, diglycol monotertiary phenylate (PhDG), dibutyl phthalate (DBP), ethylene glycol monobenzyl ether (BzG), diglycol monotertiary benzyl oxide (BzDEG), ethyleneglycol monophenylether (PhG).The boiling point of these solvents is more than 240 ℃.Therefore, if use these solvents,, when the coating operation of silk screen printing etc., easily suppress the volatilization of solvent, result is to use steadily in the long term the seal, sealing materials paste.And the affinity of diglycol monotertiary phenylate (PhDG), dibutyl phthalate (DBP), ethylene glycol monobenzyl ether (BzG), diglycol monotertiary benzyl oxide (BzDEG), ethyleneglycol monophenylether (PhG) and pigment is high.Therefore, even the addition of these solvents is a small amount of, also can suppress the situation that in the seal, sealing materials paste, pigment separates.
As mentioned above, Texacar PC, diglycol monotertiary phenylate (PhDG), dibutyl phthalate (DBP), ethylene glycol monobenzyl ether (BzG), diglycol monotertiary benzyl oxide (BzDEG), ethyleneglycol monophenylether (PhG) have the volatilization that suppresses solvent, improve the effect of the permanent stability of seal, sealing materials paste.
Preferably seal, sealing materials film (the first seal, sealing materials film and the second seal, sealing materials film) is supplied the unsticking mixture in inert atmosphere to process, and is particularly preferably supplied in N
2unsticking mixture in atmosphere is processed.Thus, easily prevent when unsticking mixture glass powder, the rotten situation of glass powder that particularly contains SnO.
The seal, sealing materials layer preferably forms along the neighboring by the sealing-in thing, in the situation that be glass substrate by the sealing-in thing, preferably along the neighboring of glass substrate and form frame-like.Thus, the zone that can accommodate between the first year becomes large.
The surface roughness Ra of seal, sealing materials layer is below 0.6 μ m, below 0.5 μ m, is particularly preferably below 0.4 μ m.Thus, the seal, sealing materials layer with by the adaptation of sealing-in thing, improved, so laser sealing-in raising, and easily after the laser sealing-in, guarantee firm sealing strength.
The surfaceness RMS of seal, sealing materials layer is below 1.0 μ m, below 0.8 μ m, is particularly preferably below 0.7 μ m.Thus, the seal, sealing materials layer with by the adaptation of sealing-in thing, improved, so laser sealing-in raising, and easily after the laser sealing-in, guarantee firm sealing strength.
Next, to having used the manufacture method above-mentioned glass substrate with the seal, sealing materials layer, electron device to describe.It should be noted that, due to the common part of the manufacture method of the electron device illustrated in the embodiment that is present in the 1st related invention, therefore directly use Fig. 2 A～D and describe.
That is, at first, as shown in Figure 2 A, on the glass substrate 11 of forming element not, coating the first coating paste, form the first seal, sealing materials film 12.Now, the first seal, sealing materials paste is along the neighboring of glass substrate 11 and applied one-tenth frame-like.Next, as shown in Fig. 2 B, on the first seal, sealing materials film 12, coating the second seal, sealing materials paste, form the second seal, sealing materials film 13.Now, the second seal, sealing materials paste is along the first seal, sealing materials film 12 and applied one-tenth frame-like.In addition, make the coating width of the first seal, sealing materials paste and the second seal, sealing materials paste roughly the same.And, make the content of the resistivity against fire filler in the second seal, sealing materials film 13 be less than the content of the resistivity against fire filler in the first seal, sealing materials film 12.Next, as shown in Figure 2 C, the stacked film of gained is burnt till, formed seal, sealing materials layer 14 on glass substrate 11.Seal, sealing materials layer 14 firmly is bonded on glass substrate 11.Then, with regard to the content of resistivity against fire filler, with the interior region of seal, sealing materials layer 14, compare, make the surf zone of seal, sealing materials layer 14 less.Finally, as shown in Figure 2 D, make to be formed with element and do not form the glass substrate 15 of seal, sealing materials layer to contact configuration with the glass substrate 1 with the seal, sealing materials layer, then carry out the laser sealing-in, make electron device.Now, from glass substrate 11 sides along seal, sealing materials layer 14 irradiating laser, glass substrate 1 and glass substrate 15 are by hermetic seal.Thus, can prevent the thermal degradation when of electronic device component, and the permanent stability of electron device improve.
The laser sealing-in is preferably carried out under inert atmosphere, particularly preferably in N
2carry out the laser sealing-in under atmosphere.Glass powder while thus, easily preventing the laser sealing-in, the rotten situation of glass powder that particularly contains SnO.
Embodiment 1
The 1st inventive embodiment is described.But following embodiment is only illustration.The 1st invention is not subject to any restriction of following embodiment.
Table 1 shows the glass powder (sample No.1～7) that contains SnO.In addition, table 2 shows and contains Bi
2o
3glass powder (sample No.8～14).
Table 1
[table 1]
[table 2]
Following operation, prepare the glass powder that contains SnO.At first, according to the glass shown in table 1, form the blending raw material, then this blending raw material is put into to alumina crucible, under nitrogen atmosphere, 900 ℃ of meltings 1 hour～2 hours.Next, use water cooled rolls to be configured as membranaceous by the melten glass of gained.Then, after using ball mill that glassy membrane is pulverized, carry out classification, obtain the glass powder that contains SnO.The granularity of the glass powder that contains SnO of gained is, median size D
50: 1.7 μ m, maximum particle diameter D
99: 5.0 μ m.
Following operation, prepare and contain Bi
2o
3glass powder.At first, according to the glass shown in table 2, form the blending raw material, then this blending raw material is put into to platinum earthenware Crucible, under air atmosphere, 1000 ℃～1100 ℃ lower meltings 1 hour～2 hours.Next, use water cooled rolls to be configured as membranaceous by the melten glass of gained.Then, after using ball mill that glassy membrane is pulverized, carry out classification, obtain containing Bi
2o
3glass powder.Gained contain Bi
2o
3the granularity of glass powder be, median size D
50: 1.2 μ m, maximum particle diameter D
99: 4.0 μ m.
About sample No.1～7, second-order transition temperature, softening temperature, thermal expansivity are estimated.The results are shown in table 1.
Second-order transition temperature is the value of using push-down TMA device to measure.
Softening temperature is the value of using large-scale DTA device to measure.In the situation that comprise the glass powder that contains SnO, at nitrogen atmosphere, measured, contain Bi comprising
2o
3the situation of glass powder under, under air atmosphere, measured, with the heat-up rates of 10 ℃/minute, from room temperature, start to measure.
Thermal expansivity is the value of using push-down TMA device to measure.It should be noted that, in the situation that the glass powder that use contains SnO will be measured temperature range and be made as 30 ℃～250 ℃, in use, contain Bi
2o
3the situation of glass powder under, will measure temperature range and be made as 30 ℃～300 ℃.
As shown in Table 1, the second-order transition temperature of sample No.1～7 is 295 ℃～334 ℃, and softening temperature is that 364 ℃～405 ℃, thermal expansivity are 96 * 10
-7/ ℃～125 * 10
-7/ ℃.
As shown in Table 1, the second-order transition temperature of sample No.8～14 is 350 ℃～365 ℃, and softening temperature is 419 ℃～435 ℃, and thermal expansivity is 98 * 10
-7/ ℃～107 * 10
-7/ ℃.
Next, according to the blending ratio shown in table 3,4, the glass powder shown in his-and-hers watches 1,2, resistivity against fire filler, pigment are as required mixed, and produce seal, sealing materials (Sample A～N).
[table 3]
[table 4]
As the resistivity against fire filler, in the situation that the glass powder that use contains SnO is used zirconium phosphate, phosphoric acid wolframic acid zirconium; Contain Bi in use
2o
3the situation of glass powder under, use trichroite.The granularity of zirconium phosphate, phosphoric acid wolframic acid zirconium is respectively, median size D
50: 1.1 μ m, maximum particle diameter D
99: 2.4 μ m.The granularity of trichroite is, median size D
50: 0.9 μ m, maximum particle diameter D99:2.1 μ m.
In the situation that the glass powder that use contains SnO is used Ketjen black (graphite) as pigment.The median size D of primary particle
50for 20nm.
About Sample A～N, thickness, the surfaceness of seal, sealing materials layer, the laser sealing-in of second-order transition temperature, softening temperature, thermal expansivity, seal, sealing materials layer are estimated.The results are shown in table 3,4.
Second-order transition temperature is the value of using push-down TMA device to measure.
Softening temperature is the value of using large-scale DTA device to measure.In the situation that comprise the glass powder that contains SnO, under nitrogen atmosphere, measured, contain Bi comprising
2o
3the situation of glass powder under, under air atmosphere, measured, with the heat-up rates of 10 ℃/minute, from room temperature, start to measure.
Thermal expansivity is the value of using push-down TMA device to measure.The glass powder that use contains SnO it should be noted that, in the situation that will be measured temperature range and be made as 30 ℃～250 ℃; Contain Bi in use
2o
3the situation of glass powder under, will measure temperature range and be made as 30 ℃～300 ℃.
Following operation, produce the seal, sealing materials paste.At first, seal, sealing materials and material containing is mixing, then further use three-roll mill mixing to even, and paste, so that viscosity reaches about 70Pas (25 ℃, shearing rate (Shear rate): 4).As the resinous principle in material containing, use polymerized thylene carbonate ethyl ester (MW:129000), as solvent composition, use Texacar PC.It should be noted that, use the material containing of the polymerized thylene carbonate ethyl ester that has dissolved 25 quality % in Texacar PC.Next, peripheral edge portion at the glass substrate (OA-10G processed of Japanese electric apparatus nitre Co., Ltd.) of indulging 40mm * horizontal 50mm * thick 0.5mm, to reach thickness: about 5 μ m, width: the mode of about 0.6mm, use the above-mentioned seal, sealing materials paste of screen printer print, then under air atmosphere, under 85 ℃, drying is 15 minutes, then under nitrogen atmosphere, at the temperature of the softening temperature of each sample+50 ℃, burn till 10 minutes, carry out the burning (processing of unsticking mixture) of the resinous principle in the seal, sealing materials paste, and seal, sealing materials is fixing, obtain having the mean thickness shown in table, surfaceness (Ra, RMS) the glass substrate with the seal, sealing materials layer.
The mean thickness of seal, sealing materials layer is to use the fixed value of non-contact type laser film thickness measuring.
The surfaceness of seal, sealing materials layer (Ra, RMS) is to use the fixed value of surfaceness instrumentation.
Then, under nitrogen atmosphere, the glass substrate (OA-10G processed of Japanese electric apparatus nitre Co., Ltd.) that to indulge 50mm * horizontal 50mm * thick 0.5mm is configured on the seal, sealing materials layer, then from the glass substrate side that is formed with the seal, sealing materials layer along the seal, sealing materials layer, under the described condition of table 2, the laser that illumination wavelength is 808nm, make the seal, sealing materials layer softening mobile, by glass substrate hermetic seal each other thus.
The sealing-in of observing after hot and humid high-potting: HAST test (Highly Accelerated Temperature and Humidity Stress test) partly has or not and peels off, thereby sealing-in is estimated to laser.It should be noted that, the condition of HAST test is: 121 ℃, humidity 100%, 2atm, 24 hours.
From table 3,4, the surface roughness Ra of the seal, sealing materials layer of Sample A～E and H～L is below 0.15 μ m, and RMS is below 0.30 μ m, the surface smoothness excellence.Consequently, with regard to Sample A～E and H～L, at all laser irradiation conditions, all glass substrate can be engaged with each other.
On the other hand, surface roughness Ra, the RMS of the seal, sealing materials layer of sample F are large, under the low output rating condition below 15W, confirm that sealing-in is partly peeled off after the HAST test.Think that the reason of this situation is, because the content of resistivity against fire filler is many, so the surface smoothness deficiency of seal, sealing materials layer, the softening mobility of seal, sealing materials is hindered.In addition, think because the content of the resistivity against fire filler of sample G is few, therefore be difficult to and matched coefficients of thermal expansion by the sealing-in thing.It should be noted that, with regard to sample G, think if use the laser of high-output power, glass substrate can be engaged with each other, but think rigidly connect close after seal interface crackle easily occurs.
Surface roughness Ra, the RMS of the seal, sealing materials layer of sample M are large, under the low output rating condition below 15W, confirm that sealing-in is partly peeled off after the HAST test.Think that the reason of this situation is, because the content of resistivity against fire filler is many, so the surface smoothness deficiency of seal, sealing materials layer, the softening mobility of seal, sealing materials is hindered.It should be noted that, with regard to sample M, due to the CuO in glass powder and Fe
2o
3total content few, therefore possibly the energy of irradiated laser fully can't be absorbed.In addition, with regard to sample N, because the content of resistivity against fire filler is few, therefore think and be difficult to coupling by the thermal expansivity of sealing-in thing.It should be noted that, with regard to sample N, think if use the laser of high-output power, glass substrate can be engaged with each other, but think engage after soon seal interface crackle easily occurs.
Embodiment 2
Below, the 2nd inventive embodiment is described.It should be noted that, following embodiment is only illustration.The 2nd invention is not subject to any restriction of following embodiment.
Table 1 shows the 2nd inventive embodiment (sample No.15～17) and comparative example (sample No.18,19).In addition, table 6 shows the 2nd inventive embodiment (sample No.20～22) and comparative example (sample No.23,24).
[table 5]
[table 6]
Following operation, prepare SnO-P
2o
5the glass frit end.At first, glass according to the rules forms (SnO59%, P in mol%,
2o
520%, ZnO5%, B
2o
315%, Al
2o
31%) the blending raw material, then put into alumina crucible by this blending raw material, and under the nitrogen atmosphere of 900 ℃, melting is 1～2 hour.Next, use water cooled rolls to be configured as membranaceous by the melten glass of gained.Then, after using ball mill that the glassy membrane of gained is pulverized, carry out air classifying, obtain glass powder.The second-order transition temperature of this glass powder is 301 ℃, and softening temperature is 385 ℃, and density is 3.88g/cm
3, median size D
50be 1.5 μ m, 90% particle diameter D
90be 3.5 μ m, 99% particle diameter D
99be 5.7 μ m.
Following operation, prepare Bi
2o
3-B
2o
3the glass frit end.At first according to the rules glass forms (Bi in mol%,
2o
337%, B
2o
326%, ZnO17.5%, CuO14%, BaO5%, Fe
2o
30.5%) the blending raw material, then put into platinum crucible by this blending raw material, and under the air atmosphere of 1000 ℃, lower melting is 1～2 hour.Next, use water cooled rolls to be configured as membranaceous by the melten glass of gained.Then, after using ball mill that the glassy membrane of gained is pulverized, carry out air classifying, obtain glass powder.The second-order transition temperature of this glass powder is 360 ℃, and softening temperature is 435 ℃, and density is 6.96g/cm
3, median size D
50be 1.1 μ m, 90% particle diameter D
90be 2.1 μ m, 99% particle diameter D
99be 2.9 μ m.
Second-order transition temperature is the value of using push-down TMA device to measure.It should be noted that, as measuring sample, use by glass powder densely after sintering, be processed into the sample of regulation shape.
Softening temperature is the value of using large-scale DTA device to measure.Using SnO-P
2o
5in the situation at glass frit end, under nitrogen atmosphere, measured, used Bi
2o
3-B
2o
3in the situation at glass frit end, under air atmosphere, measured.In addition, with the heat-up rate of 10 ℃/minute, from room temperature, start to measure.
In sample No.15～19, use zirconium phosphate as the resistivity against fire filler.The density of zirconium phosphate is 3.80g/cm
3, median size D
50be 1.6 μ m, 90% particle diameter D
90be 3.3 μ m, 99% particle diameter D
99be 5.1 μ m.
In sample No.20～24, use trichroite as the resistivity against fire filler.The density of trichroite is 2.63g/cm
3, median size D
50be 0.9 μ m, 90% particle diameter D
90be 1.8 μ m, 99% particle diameter D
99be 2.3 μ m.
As pigment, use Ketjen black (graphite).The median size D of the primary particle of pigment
50for 20nm.
Median size D
50, 90% particle diameter D
90, 99% particle diameter D99 uses the fixed value of laser diffraction formula size-grade distribution instrumentation.
In sample No.15～19, by above-mentioned SnO-P
2o
5glass frit end 60 volume % and resistivity against fire filler 40 volume % mix, and produce inorganic powder.Next, be about to inorganic powder 99.75 quality % and pigment 0.25 quality % mixing, produce seal, sealing materials.The second-order transition temperature of this seal, sealing materials is 363 ℃, and softening temperature is 430 ℃, and density is 3.85g/cm
3.
In sample No.20～24, by above-mentioned Bi
2o
3-B
2o
3glass frit end 75 volume % and resistivity against fire filler 25 volume % mix, and produce seal, sealing materials (inorganic powder).The second-order transition temperature of this seal, sealing materials is 370 ℃, and softening temperature is 450 ℃, and density is 5.88g/cm
3.
Second-order transition temperature is the value of using push-down TMA device to measure.It should be noted that, as measuring sample, use by seal, sealing materials densely after sintering, be processed into the sample of regulation shape.
Softening temperature is the value of using large-scale DTA device to measure.Using SnO-P
2o
5in the situation at glass frit end, under nitrogen atmosphere, measured; Using Bi
2o
3-B
2o
3in the situation at glass frit end, under air atmosphere, measured.In addition, with the heat-up rate of 10 ℃/minute, from room temperature, start to measure.
Following operation, produce the seal, sealing materials paste.At first, above-mentioned seal, sealing materials and material containing is mixing, then further use three-roll mill mixing to even, and paste, so that viscosity reaches about 70Pas (25 ℃, shearing rate (Shear rate): 4).Use polymerized thylene carbonate ethyl ester (MW:129000) as the resinous principle in material containing, as solvent composition, used Texacar PC.It should be noted that, use the material containing of the polymerized thylene carbonate ethyl ester that has dissolved 25 quality % in Texacar PC.Next, peripheral edge portion (33mm is square) at the glass substrate (OA-10G processed of Japanese electric apparatus nitre Co., Ltd.) of indulging 40mm * horizontal 50mm * thick 0.5mm, to reach thickness: about 10 μ m, width: the mode of about 0.6mm, use the above-mentioned seal, sealing materials paste of screen printer print, then under air atmosphere, under 85 ℃, drying is after 15 minutes, under nitrogen atmosphere, according to the condition shown in table (wherein, be warming up to room temperature with 10 ℃/minute from room temperature, and lowered the temperature with 10 ℃/minute) sample No.1～5 are burnt till, resinous principle in the seal, sealing materials paste is burned and removes, and form the seal, sealing materials layer on glass substrate.In addition, under air atmosphere, according to the condition shown in table (wherein, be warming up to room temperature with 10 ℃/minute from room temperature, and lowered the temperature with 10 ℃/minute) sample No.6～10 are burnt till, resinous principle in the seal, sealing materials paste is burned and removes, and form the seal, sealing materials layer on glass substrate.
Then, on the seal, sealing materials layer, under nitrogen atmosphere, configuration has the square Ca film of 30mm in central part vacuum evaporation in advance, and (thickness: the glass substrate of vertical 50mm about 100nm) * horizontal 50mm * thick 0.5mm (OA-10G processed of Japanese electric apparatus nitre Co., Ltd.) is so that they are overlapping, then from the glass substrate side that is formed with the seal, sealing materials layer along the seal, sealing materials layer, the laser that is 808nm according to the condition illumination wavelength shown in table, make thus the seal, sealing materials layer softening mobile, by glass substrate hermetic seal each other.
When irradiating laser irradiates, use radiation thermometer to measure the temperature of seal, sealing materials layer, and measure the laser sealing temperature.
Following operation, estimated resistance to air loss.Sample after the laser sealing-in is dropped in the drying machine be set as 85 ℃ of temperature, humidity 85% 1000 hours, observe the rotten of Ca film.To be " zero " less than the average evaluation of observing white point in the Ca film, the average evaluation that will in the Ca film, observe white point be " * ".It should be noted that, the Ca film is water white, if but the Ca film touches moisture, become white Ca (OH) 2.Therefore, can pass through to observe the variation of Ca film, thereby the resistance to air loss in sample is estimated.
From 5,6, with regard to sample No.15～17 and 20～22, in bubble-tight evaluation all less than in the Ca film, observing white point.On the other hand, with regard to sample No.18,19,23 and 24, in bubble-tight evaluation, observe the white point of several 0.5mm left and right in the Ca film.Think that the reason of this situation is, due to the laser sealing temperature higher than firing temperature, so during the laser sealing-in, H
2o gas produces and reacts with the Ca film in the seal, sealing materials layer, and has generated Ca (OH)
2.
Embodiment 3
Embodiment to the 1st related invention is elaborated.But following embodiment is only illustration.The 1st related invention is not subject to any restriction of following embodiment.
Table 7 shows size-grade distribution and the softening temperature of the glass powder A～E that contains SnO.Table 8 shows and contains Bi
2o
3size-grade distribution and the softening temperature of glass powder F～J.
[table 7]
[table 8]
Glass powder A～the E that contains SnO is prepared in following operation.At first, glass according to the rules form (in following oxide compound, convert % by mole, SnO59%, P
2o
520%, ZnO5%, B
2o
315%, Al
2o
31%) the blending raw material, then put into alumina crucible by this blending raw material, under nitrogen atmosphere, 900 ℃ of lower meltings 1 hour～2 hours.Next, use water cooled rolls to be configured as membranaceous by the melten glass of gained.Then, after using ball mill that glassy membrane is pulverized, carry out classification, obtain the glass powder A～E that contains SnO.It should be noted that, by pulverization conditions, classification condition being adjusted to, adjusted the granularity of the glass powder A～E that contains SnO.
Following operation, prepare and contain Bi
2o
3glass powder F～J.At first, glass according to the rules form (in following oxide compound, convert % by mole, Bi
2o
337%, B
2o
326%, ZnO17.5%, CuO14%, BaO5%, Fe
2o
30.5%) the blending raw material, then put into platinum crucible by this blending raw material, under air atmosphere, 1000 ℃ of lower meltings 1 hour～2 hours.Next, use water cooled rolls to be configured as membranaceous by the melten glass of gained.Then, after using ball mill that glassy membrane is pulverized, carry out classification, obtain containing Bi
2o
3glass powder F～J.It should be noted that, by pulverization conditions, classification condition are adjusted, adjust and contain Bi
2o
3the granularity of glass powder F～J.
The size-grade distribution of glass powder A～J is to use the fixed value of laser diffraction formula size-grade distribution instrumentation.
Softening temperature is the value of using large-scale DTA device to measure.The glass powder that contains SnO is measured under nitrogen atmosphere; Contain Bi
2o
3glass powder, under air atmosphere, measured.It should be noted that, be about to heat-up rate and be made as 10 ℃/minute, start to measure from room temperature.
Table 9 shows embodiment (sample No.25～29) and the comparative example (sample No.30,31) of the 1st related invention.Table 10 shows embodiment (sample No.32～36) and the comparative example (sample No.37,38) of the 1st related invention.
[table 9]
[table 10]
At first, for the glass powder that respectively contains SnO (A～E), add resistivity against fire filler, pigment and mixed, producing each related seal, sealing materials of table 9.Blending ratio is, the glass powder that contains SnO: resistivity against fire filler (volume %)=60:40, glass powder+resistivity against fire filler: pigment (quality %)=99.75:0.25.
In addition, for each Bi
2o
3contain glass powder (F～J), add the resistivity against fire filler and mixed, produce each related seal, sealing materials of table 10.Blending ratio is, contains Bi
2o
3glass powder: resistivity against fire filler (volume %)=67:33.
As the resistivity against fire filler added, use the zirconium phosphate powder in containing the glass powder of SnO.The density of zirconium phosphate is 3.80g/cm
3, granularity is, median size D
50: 1.6 μ m, 90% particle diameter D
90: 3.3 μ m, maximum particle diameter D99:5.1 μ m.As the pigment added, use Ketjen black (graphite) in containing the glass powder of SnO.The median size D of the primary particle of pigment
50for 20nm.
As containing Bi
2o
3glass powder in the resistivity against fire filler that adds, use cordierite powder.The density of trichroite is 2.63g/cm
3, granularity is, median size D
50: 1.2 μ m, 90% particle diameter D
90: 2.8 μ m, maximum particle diameter D
99: 3.5 μ m.
It should be noted that, the granularity of resistivity against fire filler, pigment is to use the fixed value of laser diffraction formula size-grade distribution instrumentation.
For each seal, sealing materials, measured thermal expansivity.
Thermal expansivity is to use push-down TMA device, the value of measuring in the temperature range of 30～300 ℃.It should be noted that, as measuring sample, make each seal, sealing materials sample after sintering densely.
Following operation, produce each seal, sealing materials paste.At first, seal, sealing materials and material containing is mixing, then further use three-roll mill mixing to evenly, and paste so that viscosity reach about 70Pas (under 25 ℃, shearing rate (Shear rate): 4).The material containing consisted of organic binder bond and solvent is used in material containing.Use the polymerized thylene carbonate ethyl ester that molecular weight is 129000 (below, be called PEC) as organic binder bond, as solvent composition, use Texacar PC (below, be called PC) and diglycol monotertiary phenylate (below, be called PhDG).It should be noted that, the mixture ratio of PC/PhDG is adjusted into to 90/10 by quality ratio.In addition, the mixture ratio of PEC/ (PC+PhDG) is adjusted into to 25/75 by quality ratio.
It should be noted that, in each seal, sealing materials paste, the condition except the granularity of glass powder is all identical.
Then, peripheral edge portion at the glass substrate (OA-10G processed of Japanese electric apparatus nitre Co., Ltd.) of indulging 40mm * horizontal 50mm * thick 0.5mm, after the first seal, sealing materials paste in using screen process press coating table, under air atmosphere, under 85 ℃, drying is 10 minutes, produces the first seal, sealing materials film (desciccator diaphragm).Next, on the first seal, sealing materials film in table, after coating the second seal, sealing materials paste, under air atmosphere, under 85 ℃, drying is 10 minutes, produces the second seal, sealing materials film (desciccator diaphragm).In the situation that the glass powder that use contains SnO, under nitrogen atmosphere, under 480 ℃, burns till the stacked film of gained 10 minutes, burn the organic binder bond in material containing, and form the seal, sealing materials layer on glass substrate.Comprise Bi in use
2o
3the situation of glass powder under, under air atmosphere, under 480 ℃, the stacked film of gained is burnt till 10 minutes, burn the organic binder bond in material containing, and form the seal, sealing materials layer on glass substrate.The surfaceness of seal, sealing materials layer has been shown in table 9,10.It should be noted that, so that the mean thickness of the seal, sealing materials layer of the first layer is 8.0 μ m, makes the mode that the mean thickness of the seal, sealing materials layer of the second layer is 12.0 μ m adjust printing condition.
The surface roughness Ra of seal, sealing materials layer, RMS are the values of measuring by the method according to JIS B0601:2001.
Then, under nitrogen atmosphere, after on seal, sealing materials, the glass substrate (OA-10G processed of Japanese electric apparatus nitre Co., Ltd.) of 50mm * horizontal 50mm * thick 0.5mm is indulged in configuration, from the glass substrate side that is formed with the seal, sealing materials layer along the seal, sealing materials layer, under the conditions shown in Table 8, the laser that illumination wavelength is 808nm, make the seal, sealing materials layer softening mobile, by glass substrate hermetic seal each other thus.It should be noted that, the irradiation speed of laser is made as to 20m/s, the temperature of the seal, sealing materials layer while using radiation thermometer to laser radiation is measured.
The sealing-in of observing after hot and humid high-potting: HAST test (Highly Accelerated Temperature and Humidity Stress test) partly has or not and peels off, thereby sealing-in is estimated to laser.It should be noted that, the condition of HAST test is: 121 ℃, humidity 100%, 2atm, 24 hours.
From table 9,10, with regard to sample No.25～29,32～36, after the HAST test, sealing-in is not partly peeled off, and can maintain resistance to air loss.In addition, with regard to sample No.25～29,32～36, the surface roughness Ra of seal, sealing materials layer is that 0.05 μ m～0.3 μ m, surfaceness RMS is 0.15 μ m～0.6 μ m, and the surface smoothness of seal, sealing materials layer is good.Consequently, because the needed laser output power of laser sealing-in reduces, so the temperature of seal, sealing materials layer during laser radiation is below 550 ℃.It should be noted that, if the excess Temperature of seal, sealing materials layer during laser radiation, metal electrode thermal degradation when, resistance easily rises.
On the other hand, with regard to sample No.30,31,37,38, confirm to divide and peel off in the rear sealed portion of HAST test.Think that the reason of this situation is, the surface smoothness deficiency of seal, sealing materials layer, even therefore make laser output power increase, also can't guarantee sufficient sealing strength.
Embodiment 4
Embodiment to the 2nd related invention describes.But following embodiment is only illustration.The 2nd related invention is not subject to any restriction of following embodiment.
Table 11,12 shows the glass constituent and properties of each glass powder (Sample A～F).
[table 11]
[table 12]
Following operation, prepare the glass powder that respectively contains SnO.At first, according to the glass in table, form the blending raw material, then this blending raw material is put into to alumina crucible, under nitrogen atmosphere, 900 ℃ of lower meltings 1 hour～2 hours.Next, use water cooled rolls to be configured as membranaceous by the melten glass of gained.Then, after using ball mill that glassy membrane is pulverized, carry out classification, obtain respectively containing the glass powder of SnO.
Following operation, prepare and respectively contain Bi
2o
3glass powder.At first, according to the glass in table, form the blending raw material, then this blending raw material is put into to alumina crucible, under nitrogen atmosphere, 1000 ℃ of lower meltings 1 hour～2 hours.Next, use water cooled rolls to be configured as membranaceous by the melten glass of gained.Then, after using ball mill that glassy membrane is pulverized, carry out classification, obtain respectively containing Bi
2o
3glass powder.
Density is to adopt Archimedes's method to measure the value that is configured as block glass and obtains.
Size-grade distribution is to use the fixed value of laser diffraction formula size-grade distribution instrumentation.
Softening temperature is the value of using large-scale DTA device to measure.In the situation that the glass powder that use contains SnO is measured under nitrogen atmosphere; Contain Bi in use
2o
3the situation of glass powder under, under air atmosphere, measured.It should be noted that, heat-up rate is made as to 10 ℃/minute, start to measure from room temperature.
Thermal expansivity refers to the value of using push-down TMA device to measure.It should be noted that, as measuring sample, use will be configured as the sample of the glass processing established practice setting shape after bulk.In addition, in the situation that the glass powder that use contains SnO will be measured temperature range and be made as 30 ℃～250 ℃; Contain Bi in use
2o
3the situation of glass powder under, will measure temperature range and be made as 30 ℃～300 ℃.
Table 13,14 shows embodiment (sample No.39,40,42,43) and the comparative example (sample No.41,44) of the 2nd related invention.
[table 13]
[table 14]
At first, for the glass powder that respectively contains SnO, add resistivity against fire filler, pigment and mixed, producing each related seal, sealing materials of table 13.Blending ratio is, the glass powder that contains SnO: resistivity against fire filler (volume %)=60:40, the glass powder+resistivity against fire filler that contains SnO: pigment (quality %)=99.75:0.25.
The related resistivity against fire filler as table 13, used the zirconium phosphate powder.The density of zirconium phosphate is 3.80g/cm
3, granularity is, median size D
50: 1.6 μ m, 90% particle diameter D
90: 3.3 μ m, maximum particle diameter D
99: 5.1 μ m.Use Ketjen black (graphite) as pigment.The median size D of the primary particle of pigment
50for 20nm.It should be noted that, the granularity of resistivity against fire filler, pigment is to use the fixed value of laser diffraction formula size-grade distribution instrumentation.
For containing Bi
2o
3glass powder, add the resistivity against fire filler and also mixed, produce each related seal, sealing materials of table 14.Blending ratio is, glass powder: resistivity against fire filler (volume %)=70:30.
The related resistivity against fire filler as table 14, used cordierite powder.The density of trichroite is 2.63g/cm
3, granularity is, median size D
50: 1.0 μ m, 90% particle diameter D
90: 2.1 μ m, maximum particle diameter D
99: 2.9 μ m.It should be noted that, the granularity of resistivity against fire filler is to use the fixed value of laser diffraction formula size-grade distribution instrumentation.
For each seal, sealing materials, measure thermal expansivity.
The value that thermal expansivity is private push-down TMA device, measure the temperature ranges of 30～300 ℃.It should be noted that, as measuring sample, make each seal, sealing materials sample that sintering forms densely.
Following operation, produce each seal, sealing materials paste.At first, seal, sealing materials and material containing is mixing, then further use three-roll mill mixing to even, and paste, so that viscosity reaches about 70Pas (25 ℃, shearing rate (Shear rate): 4).The material containing consisted of organic binder bond and solvent is used in material containing.The polymerized thylene carbonate ethyl ester that is 129000 as organic binder bond use molecular weight (below, be called PEC); Use Texacar PC (below, be called PC) and diglycol monotertiary phenylate (below, be called PhDG) as solvent composition.It should be noted that, the mixture ratio of PC/PhDG is adjusted to 90/10 by quality ratio.In addition, the mixture ratio of PEC/ (PC+PhDG) is adjusted into to 25/75 by quality ratio.
It should be noted that, in each seal, sealing materials paste, make glass powder condition in addition identical.
Then, peripheral edge portion at the glass substrate (OA-10G processed of Japanese electric apparatus nitre Co., Ltd.) of indulging 40mm * horizontal 50mm * thick 0.5mm, after the first seal, sealing materials paste in using screen process press coating table, under air atmosphere, under 85 ℃, drying is 10 minutes, produces the first seal, sealing materials film (desciccator diaphragm).Next, on the first seal, sealing materials film in table, after coating the second seal, sealing materials paste, under air atmosphere, under 85 ℃, drying is 10 minutes, produces the second seal, sealing materials film (desciccator diaphragm).In the situation that the glass powder that use contains SnO, under nitrogen atmosphere, under 480 ℃, burns till the stacked film of gained 10 minutes, burn the organic binder bond in material containing, and form the seal, sealing materials layer on glass substrate.Contain Bi in use
2o
3the situation of glass powder under, under air atmosphere, under 480 ℃, the stacked film of gained is burnt till 10 minutes, burn the organic binder bond in material containing, form the seal, sealing materials layer on glass substrate.The surfaceness of seal, sealing materials layer has been shown in table 13,14.It should be noted that, so that the mean thickness of the seal, sealing materials layer of the first sublevel is 8.0 μ m, the mode that the mean thickness that makes the seal, sealing materials layer of the second layer is 12.0 μ m is adjusted printing condition.
The surface roughness Ra of seal, sealing materials layer, RMS are the values of measuring by the method according to JIS B0601:2001.
Then, under nitrogen atmosphere, after on the seal, sealing materials layer, the glass substrate (OA-10G processed of Japanese electric apparatus nitre Co., Ltd.) of 50mm * horizontal 50mm * thick 0.5mm is indulged in configuration, from the glass substrate side that is formed with the seal, sealing materials layer along the seal, sealing materials layer, under the condition shown in table 13,14, the laser that illumination wavelength is 808nm, make the seal, sealing materials layer softening mobile, by glass substrate hermetic seal each other.It should be noted that, the irradiation speed of laser is made as to 20m/s, the temperature of the seal, sealing materials layer while using radiation thermometer to measure laser radiation.
The sealing-in of observing after hot and humid high-potting: HAST test (Highly Accelerated Temperature and Humidity Stress test) partly has or not and peels off, thereby sealing-in is estimated to laser.It should be noted that, the condition of HAST test is: 121 ℃, humidity 100%, 2atm, 24 hours.
From table 13,14, with regard to sample No.39,40,42,43, after the HAST test, sealing-in is not partly peeled off, and can maintain resistance to air loss.In addition, with regard to sample No.39,40,42,43, the surface roughness Ra of seal, sealing materials layer be respectively 0.4 μ m, 0.3 μ m,, 0.15 μ m, 0.1 μ m, surfaceness RMS is respectively 0.8 μ m, 0.7 μ m, 0.3 μ m, 0.2 μ m, the surface smoothness of seal, sealing materials layer is good.And result is, because the needed laser output power of laser sealing-in reduces, so the temperature of seal, sealing materials layer during laser radiation is below 550 ℃.It should be noted that, if the excess Temperature of seal, sealing materials layer during laser radiation, metal electrode thermal degradation when, resistance easily rises.
On the other hand, with regard to sample No.41,44, confirm to divide and peel off in the rear sealed portion of HAST test.Think that the reason of this situation is, the surface smoothness deficiency of seal, sealing materials layer, even therefore make laser output power increase, also can't guarantee sufficient sealing strength.
Embodiment 5
Embodiment to the 3rd related invention describes.But following embodiment is only illustration.The 3rd related invention is not subject to any restriction of following embodiment.
Table 15 shows embodiment (sample No.45～49) and the comparative example (sample No.50,51) of the 3rd related invention.Table 16 shows embodiments of the invention (sample No.52～56) and comparative example (sample No.57,58).
Table 15
[table 15]
[table 16]
Following operation, prepare the glass powder that contains SnO.At first, glass according to the rules forms (SnO59%, P in mol%,
2o
520%, ZnO5%, B
2o
315%, Al
2o
31%) the mediation raw material, then put into alumina crucible by this blending raw material, under nitrogen atmosphere, 900 ℃ of lower meltings 1 hour～2 hours.Next, use water cooled rolls to be configured as membranaceous by the melten glass of gained.Then, after using ball mill that glassy membrane is pulverized, carry out classification, obtain glass powder.The density of the glass powder that contains SnO is 3.88g/cm
3, the granularity of the glass powder that contains SnO is, median size D
50: 1.5 μ m, 90% particle diameter D
90: 3.5 μ m, maximum particle diameter D
99: 5.7 μ m.
Following operation, prepare and contain Bi
2o
3glass powder.At first, glass according to the rules forms (Bi in mol%,
2o
337%, B
2o
326%, ZnO17.5%, CuO14%, BaO5%, Fe
2o
30.5%) the mediation raw material, then put into platinum crucible by this blending raw material, under air atmosphere, 1000 ℃ of lower meltings 1 hour～2 hours.Next, use water cooled rolls to be configured as membranaceous by the melten glass of gained.Then, after using ball mill that glassy membrane is pulverized, carry out classification, obtain containing Bi
2o
3glass powder.The density of glass powder is 6.99g/cm
3, contain Bi
2o
3the granularity of glass powder be, median size D
50: 1.3 μ m, 90% particle diameter D
90: 3.1 μ m, maximum particle diameter D
99: 4.7 μ m.
The related resistivity against fire filler as table 15, used zirconium phosphate.The density of zirconium phosphate is 3.80g/cm
3, its granularity is, median size D
50: 1.6 μ m, 90% particle diameter D
90: 3.3 μ m, maximum particle diameter D
99: 5.1 μ m.
The related resistivity against fire filler as table 16, used trichroite.The density of trichroite is 2.63g/cm
3, its granularity is, median size D50:1.0 μ m, 90% particle diameter D90:2.2 μ m, maximum particle diameter D99:2.9 μ m.
As pigment, use Ketjen black (graphite).The median size D of the primary particle of pigment
50for 20nm.
The glass powder that contains SnO, contain Bi
2o
3glass powder, resistivity against fire filler, the granularity of pigment be to use the fixed value of laser diffraction formula size-grade distribution instrumentation.
To contain the glass powder of SnO+resistivity against fire filler (the total content of the glass powder that contains SnO and resistivity against fire filler) 99.75 quality % and pigment 0.25 quality % mixes, produce the related seal, sealing materials of table 15.It should be noted that, the blending ratio of the glass powder that contains SnO and resistivity against fire filler is as shown in Table 15.
To contain Bi
2o
3glass powder and resistivity against fire filler mix, produce the related seal, sealing materials of table 16.Contain Bi
2o
3glass powder and the blending ratio of resistivity against fire filler shown in table 16.
For the seal, sealing materials of gained, measure thermal expansivity.Thermal expansivity is the value of using push-down TMA device, being measured the temperature range of 30～300 ℃.It should be noted that, as measuring sample, each seal, sealing materials sample of sintering densely during use.
Following operation, produce the seal, sealing materials paste.At first, seal, sealing materials and material containing is mixing, then further use three-roll mill mixing to even, and paste, so that viscosity reaches about 70Pas (25 ℃, shearing rate (Shear rate): 4).The material containing consisted of organic binder bond and solvent is used in material containing.As organic binder bond, the polymerized thylene carbonate ethyl ester that the use molecular weight is 129000 (below, be called PEC), as solvent composition, the use Texacar PC (below, be called PC) and the diglycol monotertiary phenylate (below, be called PhDG).It should be noted that, the mixture ratio of PC/PhDG is adjusted into to 90/10 by quality ratio.In addition, the mixture ratio of PEC/ (PC+PhDG) is adjusted into to 25/75 by quality ratio.
It should be noted that, in each seal, sealing materials paste, make the condition except the blending ratio of glass powder and resistivity against fire filler identical.
Then, peripheral edge portion at the glass substrate (OA-10G processed of Japanese electric apparatus nitre Co., Ltd.) of indulging 40mm * horizontal 50mm * thick 0.5mm, after the first seal, sealing materials paste in using screen process press coating table, under air atmosphere, under 85 ℃, drying is 10 minutes, produces the first seal, sealing materials film (desciccator diaphragm).Next, on the first seal, sealing materials film in table, after coating the second seal, sealing materials paste, under air atmosphere, under 85 ℃, drying is 10 minutes, produces the second seal, sealing materials film (desciccator diaphragm).In the situation that the glass powder that use contains SnO, under nitrogen atmosphere, under 480 ℃, burns till the stacked film of gained 10 minutes, burn the organic binder bond in material containing, and form the seal, sealing materials layer on glass substrate.Contain Bi in use
2o
3the situation of glass powder under, under air atmosphere, under 480 ℃, the stacked film of gained is burnt till 10 minutes, burn the organic binder bond in material containing, and form the seal, sealing materials layer on glass substrate.The surfaceness of seal, sealing materials layer has been shown in table 15,16.It should be noted that, so that the mean thickness of the seal, sealing materials layer of the first layer is 8.0 μ m, makes the mode that the mean thickness of the seal, sealing materials layer of the second layer is 12.0 μ m adjust printing condition etc.
The surface roughness Ra of seal, sealing materials layer, RMS are the values of measuring by the method according to JIS B0601:2001.
Then, under nitrogen atmosphere, after on the seal, sealing materials layer, the glass substrate (OA-10G processed of Japanese electric apparatus nitre Co., Ltd.) of 50mm * horizontal 50mm * thick 0.5mm is indulged in configuration, from the glass substrate side that is formed with the seal, sealing materials layer along the seal, sealing materials layer, under the condition shown in table, the laser that illumination wavelength is 808nm, make the seal, sealing materials layer softening mobile, by glass substrate hermetic seal each other thus.It should be noted that, the irradiation speed of laser is made as to 20m/s, the temperature of the seal, sealing materials layer while using radiation thermometer to laser radiation is measured.
The sealing-in of observing after hot and humid high-potting: HAST test (Highly Accelerated Temperature and Humidity Stress test) partly has or not and peels off, thereby sealing-in is estimated to laser.It should be noted that, the condition of HAST test is: 121 ℃, humidity 100%, 2atm, 24 hours.
From table 15,16, with regard to sample No.45～49,52～56, after the HAST test, sealing-in is not partly peeled off, and can maintain resistance to air loss.In addition, with regard to sample No.45～49,52～56, the surface roughness Ra of seal, sealing materials layer is 0.01 μ m～0.22 μ m, and surfaceness RMS is 0.03 μ m～0.49 μ m, and the surface smoothness of seal, sealing materials layer is good.Consequently, because the needed laser output power of laser sealing-in reduces, so the temperature of seal, sealing materials layer during laser radiation is below 550 ℃.It should be noted that, if the excess Temperature of seal, sealing materials layer during laser radiation, metal electrode thermal degradation when, resistance easily rises.
On the other hand, with regard to sample No.50,51,57,58, confirm to divide and peel off in the rear sealed portion of HAST test.Think that the reason of this situation is, the surface smoothness deficiency of seal, sealing materials layer, even therefore laser output power rises, also can't guarantee sufficient sealing strength.
Utilizability on industry
Glass substrate with the seal, sealing materials layer of the present invention, except being applicable to organic EL device, also is applicable to the laser sealing-in of the solar cell of dye-sensitized solar cell etc., the laser sealing-in of lithium-ion secondary cell, the laser sealing-in of MEMS encapsulation etc.
In addition, the manufacture method of electron device of the present invention, except being applicable to organic EL device, also is applicable to the manufacture method of the solar cell, lithium-ion secondary cell, MEMS encapsulation etc. of dye-sensitized solar cell etc.
Nomenclature
1 glass substrate with the seal, sealing materials layer
11 glass substrates
12 first seal, sealing materials films
13 second seal, sealing materials films
14 seal, sealing materials layers
15 glass substrates
Claims (28)
1. the glass substrate with the seal, sealing materials layer, it possesses the seal, sealing materials layer made after the seal, sealing materials sintering, it is characterized in that,
Described seal, sealing materials at least comprises inorganic powder,
Described inorganic powder comprises glass powder and resistivity against fire filler,
The content of the resistivity against fire filler in described inorganic powder is 10 volume %～35 volume %,
The surface roughness Ra of described seal, sealing materials layer is less than 0.5 μ m.
2. the glass substrate with the seal, sealing materials layer, it possesses the seal, sealing materials layer made after the seal, sealing materials sintering, it is characterized in that,
Described seal, sealing materials at least comprises inorganic powder,
Described inorganic powder comprises glass powder and resistivity against fire filler,
The content of the resistivity against fire filler in described inorganic powder is 10 volume %～35 volume %,
The surfaceness RMS of described seal, sealing materials layer is less than 1.0 μ m.
3. the glass substrate with the seal, sealing materials layer according to claim 1 and 2, is characterized in that, the mean thickness of described seal, sealing materials layer is less than 10 μ m.
4. according to the described glass substrate with the seal, sealing materials layer of any one in claim 1～3, it is characterized in that, does not grind on the surface of described seal, sealing materials layer.
5. according to the described glass substrate with the seal, sealing materials layer of any one in claim 1～4, it is characterized in that, described glass powder is the glass powder that contains SnO.
6. according to the described glass substrate with the seal, sealing materials layer of any one in claim 1～4, it is characterized in that, described glass powder forms in following oxide compound and converts and contain 35%～70% SnO, 10%～30% P as glass
2o
5.
7. according to the described glass substrate with the seal, sealing materials layer of any one in claim 1～4, it is characterized in that, described glass powder is for containing Bi
2o
3glass powder.
8. according to the described glass substrate with the seal, sealing materials layer of any one in claim 1～4, it is characterized in that, described glass powder forms in following oxide compound and converts and contain 20%～60% Bi as glass
2o
3, 10%～35% B
2o
3, 5%～40% ZnO, 5%～30% CuO+Fe
2o
3.
9. according to the described glass substrate with the seal, sealing materials layer of any one in claim 1～8, it is characterized in that the median size D of described resistivity against fire filler
50be below 5 μ m.
10. according to the described glass substrate with the seal, sealing materials layer of any one in claim 1～9, it is characterized in that the maximum particle diameter D of described resistivity against fire filler
99be less than 10 μ m.
11. according to the described glass substrate with the seal, sealing materials layer of any one in claim 1～10, it is characterized in that, described resistivity against fire filler is for selecting white trichroite, zircon, stannic oxide, niobium oxides, zirconium phosphate system pottery, NbZr (PO
4)
3in one or more.
12. according to the described glass substrate with the seal, sealing materials layer of any one in claim 1～11, it is characterized in that, described seal, sealing materials also comprises pigment, this pigment is carbon.
13. the glass substrate with the seal, sealing materials layer according to claim 12, is characterized in that, the content of the pigment in described seal, sealing materials is 0.2 quality %～0.7 quality %.
14. according to the described glass substrate with the seal, sealing materials layer of any one in claim 1～13, it is characterized in that, it is for the sealing-in of organic electroluminescence device.
15. according to the described glass substrate with the seal, sealing materials layer of any one in claim 1～14, it is characterized in that, it is for the laser sealing-in.
16. according to the described glass substrate with the seal, sealing materials layer of any one in claim 1～15, it is characterized in that, it is for the laser sealing-in under inert atmosphere.
17. an organic electroluminescence device, is characterized in that, its right to use requires the described glass substrate with the seal, sealing materials layer of any one in 1～16 to make.
18. the manufacture method of an electron device, it is the method for electron device of manufacturing by the laser sealing-in, it is characterized in that, comprises following operation:
Prepare the operation of glass substrate;
The material containing that will comprise the seal, sealing materials of glass powder and comprise organic binder bond mixes, and makes the operation of seal, sealing materials paste;
On described glass substrate, the described seal, sealing materials paste of coating forms the operation of coating layer;
Described coating layer is burnt till, obtained the operation with the glass substrate of seal, sealing materials layer;
Across described seal, sealing materials layer, the operation that the described glass substrate with the seal, sealing materials layer is overlapped with the glass substrate that does not form the seal, sealing materials layer; And
Reach the mode irradiating laser below firing temperature with the laser sealing temperature, make the described glass substrate with the seal, sealing materials layer and do not form the operation of the glass substrate hermetic seal of described seal, sealing materials layer.
19. the manufacture method of electron device according to claim 18, is characterized in that, described laser sealing temperature is below 500 ℃.
20. the manufacture method according to claim 18 or 19 described electron devices, is characterized in that, the inorganic powder that comprises described glass powder that described seal, sealing materials contains 97.5 quality %～100 quality % and the pigment of 0 quality %～2.5 quality %.
21. the manufacture method according to the described electron device of any one in claim 18～20, is characterized in that, described glass powder as glass form in following oxide compound, convert % by mole, contain 35%～70% SnO, 10%～30% P
2o
5.
22. the manufacture method according to the described electron device of any one in claim 18～21, is characterized in that, described glass powder as glass form in following oxide compound, convert % by mole, contain 20%～60% Bi
2o
3, 10%～35% B
2o
3, 5%～40% ZnO, 5%～30% CuO+Fe
2o
3.
23. the manufacture method according to the described electron device of any one in claim 18～22, is characterized in that, described pigment is for selecting white carbon C, Co
3o
4, CuO, Cr
2o
3, Fe
2o
3, MnO
2, SnO, Ti
no
2n-1, one or more in the spinel system complex oxide, wherein n is integer.
24. the manufacture method according to the described electron device of any one in claim 18～23, is characterized in that, described inorganic powder also comprises the resistivity against fire filler of 0.1 volume %～60 volume %.
25. the manufacture method according to the described electron device of any one in claim 18～24, is characterized in that, described electron device is organic electroluminescence device.
26. the manufacture method according to the described electron device of any one in claim 18～25, is characterized in that, described organic binder bond is aliphatic poly ethylene series carbonic ether.
27. the manufacture method according to the described electron device of any one in claim 18～26, is characterized in that, carries out burning till of described coating layer under inert atmosphere.
28. an electron device, is characterized in that, its manufacture method by the described electron device of any one in claim 18～27 is made.
Applications Claiming Priority (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011164675 | 2011-07-27 | ||
| JP2011-164675 | 2011-07-27 | ||
| JP2011-166499 | 2011-07-29 | ||
| JP2011-166542 | 2011-07-29 | ||
| JP2011-166218 | 2011-07-29 | ||
| JP2011166542 | 2011-07-29 | ||
| JP2011166499 | 2011-07-29 | ||
| JP2011166218 | 2011-07-29 | ||
| JP2011-180030 | 2011-08-21 | ||
| JP2011180030 | 2011-08-21 | ||
| PCT/JP2012/069182 WO2013015414A1 (en) | 2011-07-27 | 2012-07-27 | Glass substrate with sealing material layer, organic el device using same, and manufacturing method for electronic device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103459341A true CN103459341A (en) | 2013-12-18 |
| CN103459341B CN103459341B (en) | 2016-05-11 |
Family
ID=47601245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280018013.0A Expired - Fee Related CN103459341B (en) | 2011-07-27 | 2012-07-27 | With the glass substrate of seal, sealing materials layer, use the manufacture method of its organic EL device and electronic device |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US9469562B2 (en) |
| KR (1) | KR101477044B1 (en) |
| CN (1) | CN103459341B (en) |
| WO (1) | WO2013015414A1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| US9469562B2 (en) | 2016-10-18 |
| US20140196502A1 (en) | 2014-07-17 |
| KR20130133852A (en) | 2013-12-09 |
| WO2013015414A1 (en) | 2013-01-31 |
| KR101477044B1 (en) | 2014-12-29 |
| CN103459341B (en) | 2016-05-11 |
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